PHOTOPHYSICAL PROPERTIES OF METALLOTETRAPHENYLTETRABENZOPORPHYRINS: INSIGHTS FROM EXPERIMENTAL AND THEORETICAL STUDIES

G. V. Nepali Rajapakse

A Dissertation Submitted to the Graduate College of Bowling Green State University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY August 2008 Committee: Michael A. J. Rodgers, Advisor Sri Kolla Graduate Faculty Representative Michael Y. Ogawa Deanne L. Snavely

ii

ABSTRACT

Michael A. J. Rodgers, Advisor

Porphyrins are the most widely studied tetrapyrrole-macrocycles because of their diverse structures with unique properties and wide distribution in nature. Variations of the peripheral substituents on the porphyrin ring and the insertion/change of metal atoms into the macrocycle usually change the visible absorption spectrum. For this reason, in recent years, (metallo)porphyrins have become of major interest for applications in opto-electronics, data storage, solar cells and photomedicine. Metallo-tetraphenyltetrabenzoporphyrins (MTPTBPs) are different from other porphyrins because of the combination of electronic and structural factors, such as extension of the -system, meso-substitution and highly distorted macrocycle. Recent development in photothermal therapy (PTT) has drawn extra attention to this type of molecules. For a compound to be an effective photothermal agent, it should possess high photostability, high molar absorption coefficient in the red spectral region and fast radiationless decay of the excited states, converting the photon energy into the thermal event. Metallotetrapyrroles with first row transition metal centers have been shown to undergo fast radiationless deactivation of their excited states since the metal incorporated into the macrocycle cavity introduces a manifold of electronic states with metal-centered and/or metal+system character, some of which can be situated at lower energy than the pure ,* states that are populated by a photo-excitation process. These low-lying states provide rapid non-radiative channels for the excited deactivation, which is an optimum situation for PTT. Within this context, this dissertation has focused on tetrabenzoporphyrins coordinated with different metals to investigate central metal effects on the photophysical properties. Special attention has given to first row transition metals Cr(III), Mn(III), Co(II), Cu(II) and

iii Zn(II) while 3rd row Pt (II), analogue has been studied for comparison purposes. Only the theoretical investigations of Ni(II) and Pd(II) analogues have performed to give a full picture about the nature of the deactivation mechanism. Previously, Ni(II)TPTBP has studied in this laboratory in both experimental and theoretical points of view. Zn(II)TPTBP was investigated in order to provide experimental evidence for the spectral properties of the -localized singlet and triplet states of the tetrapyrrole macrocycle. It showed that the formation of the singlet (,*) state decayed through fluorescence to the ground state and the intersystem crossing to the triplet state(,*). The produced singlet state was vibrationally hot and after cooling it decayed to the triplet state having ca. 340 ps lifetime in pyridine. Triplet state of Zn(II)TPTBP deactivated to the ground state with ca. 236 s lifetime in pyridine. Compared with Zn(II)TPTBP, Pt(II)TPTBP showed that localized S1 state undergoes fast intersystem crossing (ca.500 fs lifetime) to triplet state. Low fluorescence quantum yield (0.0003) was observed compare to Zn analogue and it showed a high yield of phosphorescence. The triplet state lifetime found to be ca. 41 s and it was shorter than Zn(II) triplet state showing that faster intersystem crossing initiated from the spin orbit interaction introduced by heavy Pt atom in the third row transition series. Co(II), Cu(II) ,Mn(II), Cr(II) has introduced different features to the picture of the excited state deactivation mechanism having initiated by the unpaired metal electron. Co(II)TPTBP, excited singlet (,*) has converted to the localized triplet state within the instrument response time and then it was converted to hot d,d state, wherein intramolecular cooling has occurred and completed within 3 ps. After cooling the d,d state decayed into the ground state in an exponential manner having 17 ps lifetime in hexane solution. The TDDFT results indicated that the lowest d,d transition arises from a fully occupied metal d orbital to a partially occupied metal dz2 orbital and could be responsible for the observed d,d state. Cu(II)TPTBP ground state repopulation was occurred through the set of trip-doublet 2T1 and

iv trip-quartet 4T1 states which is in a equilibrium via a lower lying LMCT states. The dependence of the observed lifetime on solvent polarity confirmed the participation of the LMCT states in the overall deactivation process. The repopulation was completed within 500 ps in toluene solution. After 640 nm excitation in Cr()TPTBPCl, the S1 state underwent fast intersystem crossing (4S14T1) within a very short period of time (ca.0.05 ps lifetime) to 4T1 state. The 4T1 state of Cr()TPTBPCl in toluene deactivated with a lifetime of 224 ps, resulting the
4

T1 6T1 equilibrium. In Mn()TPTBPCl, the excited singquintet, 5S1(,*) state deactivated to the

tripquintet, 5T1(,*) within the instrument response time. After short time period, it generated the hot d,d state wherein cooling had occurred within 4 ps and cooled d,d state repopulated the ground state having 120 ps lifetime in toluene. Transient absorption spectrometry with femtosecond and nanosecond time resolution has been employed along with DFT/TDDFT theoretical examinations to investigate the sequence of events that follow Q band photo-excitation. Overall, the results of the present investigation reported a complete picture of the nature and energies of all electronic states induced by the different metals on the photophysical properties tetraphenytetrabenzoporphyrins.

To my parents

vi ACKNOWLEDGMENTS The years of graduate studies have been the most fruitful period of my life. During this period, I have grown both as a scientist and as a person. All the experience I gained from here helped me develop into the person I am now. Bowling Green was my home away from home. I would like to acknowledge all those that helped with this adventure by shining the light on my path and making sure that I did not get lost. My heartiest and foremost gratitude goes to my adviser Dr. Michael A. J. Rodgers. You paved the way for my career. Your support, guidance and encouragement helped me to develop myself as a scientist as well as a strong person to be able to face the challenges in this society. Dr. Rodgers, thank you very much for believing in me and giving me the freedom to work independently. I am sure the experience of having you as a great adviser will be in my mind for the rest of my life. I would like to extend my gratitude to my committee, Dr. Michael Ogawa, Dr. Deanne Snavely and Dr. Sri Kolla. You have supported me in enormous ways. You were with me when I was in trouble and I am fortunate to have all of you as my committee members. My special thanks go to Dr. Alexandra Soldatova for giving me a jump start to my research career. I really appreciate all of your help to succeed my thesis work within a very short period of time. I have learned so many things from you and I hope your valuable advice as a colleague and friend will continue in the future. I would like to thank the Department of Chemistry and the Center for Photochemical Sciences for giving me this great opportunity to pursue my Ph.D. career. Especially, I want to thank Nora and Alita for your valuable advice and for making the department a warm and friendly place. Also I want to thank Doug, Craig and Larry for their technical support. Also, thank you to all the members of Dr. Rodgers group, past and present. Special thanks go to Dr. Eugene Danilov.

vii Apart from making a way for my career, the other most important asset Ive gained here was my friends. I want to thank all of my friends who helped me make my journey at BG a pleasant and enjoyable place. Especially, I want to thank Chinthaka, Atty and Lilani for sharing my sorrows and laughter together. I wish to express my deepest thanks to my parents without whom I would not be the person I am now. Your inspiration and encouragement helped me to succeed and I hope I made your dream come true.

viii TABLE OF CONTENTS Page CHAPTER I. INTRODUCTION.......................................................................................... Basic Photophysics .................................................................................................... Electronic structure of Metallotetrapyrroles .............................................................. Metal-Macrocycle interaction and UV-visible spectra ................................. Metallotetrapyrroles: Background ............................................................................. Bond-Type in metalloporphyrins ................................................................... Symmetry in Metalloporphyrins..................................................................... Excited states of porphyrins and characterization of excited states of Porphyrins............................................................................................................. ,* state of the ring ...................................................................................... d,d ligand field states ..................................................................................... (,d) and (d, *) metal ring CT states....................................................... Use of tetrapyrrolic photosensitizers for cancer treatment ........................................ The effect of the extension of porphyrin ring and meso-phenyl substitution ............ Effect of saddling ........................................................................................... DFT/TDDFT Methods: Background ......................................................................... Glossary of acronyms ................................................................................................ References .................................................................................................................. CHAPTER II. MATERIALS AND METHODS.................................................................. Materials .................................................................................................................... Instrumentation and Methods .................................................................................... UV-visible Absorption Spectrometry ............................................................. Steady-State Fluorescence Spectroscopy....................................................... Femtosecond Transient Absorption Spectroscopy......................................... 15 15 16 16 17 20 21 22 24 24 30 30 30 30 31 31 1 1 2 2 8 13 14

ix Nanosecond transient Absorption.................................................................. Computational Details ............................................................................................... Estimation of the MTPTBP triplet (,*) energies from the oxygen quenching bimolecular rate constant ........................................................................................... References ................................................................................................................ CHAPTER III. THE PHOTOPHYSICAL PROPERTIES OF ZINC AND NICKEL TETRAPHNYLTETRABENZOPORPHYRINS: A COMBINED EXPERIMENTAL AND THEORETICAL INVESTIGATION........................................................................... Abstract ................................................................................................................... Introduction................................................................................................................ Theoretical characterization of Zn()TPTBP............................................................ Ground State Molecular Structure Analysis.................................................. Ground State Electronic Structure Analysis.................................................. Excited States and Ground State Absorption Spectra ................................... Optically Silent Excited States Below the S1(*) State ................................ Steady-State Fluorescence and Transient Absorption Experiments .......................... Steady-State Fluorescence Measurements..................................................... Transient Absorption Experiments ............................................................................ Femtosecond Transient Absorption ............................................................... Nanosecond Transient Absorption Experiment ............................................. Summary and Conclusions ........................................................................................ References .................................................................................................................. 41 41 41 44 44 46 48 50 51 51 53 53 59 61 62 38 39 34 36

x CHAPTER IV. THE PHOTOPHYSICAL BEHAVIOR OF OPEN-SHELL FIRST-ROW TRANSITION METAL TETRAPHENYLTETRABENZOPORPHYRINS: COPPER AND COBALT ..................................................................................................................... Abstract ..................................................................................................................... Introduction................................................................................................................ Theoretical characterization of Co()TPTBP and Cu()TPTBP.............................. Ground State Molecular Structure Analysis.................................................. Ground State Electronic Structure Analysis.................................................. a) HOMO and LUMO relative positions ........................................... b) the metal d levels ........................................................................... c) Spin unrestricted calculations ....................................................... Excited States and Ground State Absorption Spectra ................................... Ground State Absorption Spectra ...................................................... Excited States Below the S1(,*)State .............................................. Transient Absorption Experiments: Spectral observations and Dynamic properties.................................................................................................... Co()TPTBP in Hexane ................................................................................ Cu()TPTBP in Toluene................................................................................ Cu(II)TPTBP in Benzonitrile ......................................................................... Summary and Conclusions ........................................................................................ References .................................................................................................................. CHAPTER V. THE PHOTOPHYSICAL PROPERTIES OF CHROMIUM() AND MANGANESE() TETRAPHNYLTETRABENZOPORPHYRINS: AN INSIGHT INTO EXCITED STATE DECAYDYNAMICS .................................................................. Abstract ...................................................................................................................... Introduction ............................................................................................................... 97 97 98 82 82 87 88 93 94 67 67 68 70 71 72 73 75 76 77 77 79

xi Photophysical Properties of Cr()TPTBPCl............................................................ 101 Ground State Absorption Spectra .................................................................. 101 Transient Absorption: Spectral Observations and Dynamic Properties of Cr()TPTBPCl ............................................................................................. 103 Cr()TPTBPCl in toluene and DMF................................................ 103 Cr()TPTBPCl in Benzonitrile ........................................................ 106 Photophysical Properties of Mn()TPTBPCl ......................................................... 108 Ground State Absorption Spectra ..................................................................... Transient Absorption: Spectral Observations and Dynamic properties of Mn()TPTBPCl ............................................................................................... 110 108

Mn()TPTBPCl in Toluene .......................................................................... 110 Mn()TPTBPCl in Benzonitrile ................................................................... 113 Summary and Conclusions ........................................................................................ 115 References .................................................................................................................. 116 CHAPTER VI.HEAVY METAL EFFECT ON THE PHOTOPHYSICAL PROPERTIES OF PLATINUM TETRAPHYNEYTETRABENZOPORPHYRINS: INSIGHT FROM EXPERIMENTAL AND RELATIVISTIC DFT/TDDFT STUDIES ...... 118 Abstract ..................................................................................................................... 118 Introduction................................................................................................................ 118 Theoretical characterization of Pt()TPTBP: heavy- metal effect............................ 121 Ground State Molecular Structure Analysis.................................................. 121 Ground State Electronic Structure Analysis.................................................. 124 a) HOMO and LUMO relative positions ........................................... 124 b) the metal d levels ........................................................................... 127 Excited States and Ground State Absorption Spectra ................................... 128 Ground State Absorption Spectra ...................................................... 128

xii Optically Silent Excited States Below the S1(*) State .................... 131 Steady State Luminescence and Transient Absorption Experiments ........................ 131 Steady State Luminescence ............................................................................ 131 Transient Absorption Experiments ................................................................ 134 Femtosecond Transient Absorption ................................................... 134 Nanosecond Transient Absorption..................................................... 136 Oxygen quenching of the triplet state ........................................................................ 139 Summary and Conclusions ................................................................ 140 References.......................................................................................... 142 CHAPTER VII. CONCLUSIONS ......................................................................................... 145 APPENDIX A: ENERGIES AND PERCENTAGE COMPOSITION OF THE HIGHEST OCCUPIED AND LOWEST UNOCCUPIED MOLECULAR ORBITALS OF M()TPTBP, M= Zn, Co, Cu, Pt, Pd EXPRESSED INTERMS OF INDIVIDUAL ATOMS.................................................................................................... 148

xiii LIST OF FIGURES Page 1.1 Jablonski diagram to depict the energy relationship and rate processes between electronic states .......................................................................................... 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 Structures of different types of tetrapyrrole macrocycles.......................................... Porphyrin HOMOs and LUMOs................................................................................ Schematic Orbital diagram showing possible transitions .......................................... A typical absorption spectrum of a metalloporphyrin ............................................... Origin of the hypsochromic shift of the Q band ........................................................ d metal orbitals in porphyrins .................................................................................... Mechanism of action of PDT..................................................................................... Definition of rotation angle of the phenyl plane between an upward tilted pyrrole and a downward tilted pyrrole ............................................................. 2.1 2.2 3.1 3.2 3.3 3.4 The schematic representation of the ultrafast transient absorption setup .................. Schematic diagram of the nanosecond laser flash photolysis system........................ Top view of the DFT-optimized molecular structure of Zn()TPTBP ..................... Energy level scheme for Zn()TPTBP and Ni()TPTBP......................................... Contour plots of the Zn()TPTBP, together with the energy levels ......................... Ground state absorption spectra of M()TPTBP complexes in toluene M= Zn, Ni .................................................................................................................. 3.5 Normalized absorption and steady state fluorescence spectra of Zn()TPTBP in pyridine at room temperature................................................................................. 3.6 3.7 Femtosecond transient absorption difference spectra of Zn()TPTBP in pyridine .. Femtosecond transient absorption difference spectra of Zn()TPTBP in benzonitrile at 2 ps and 1000 ps................................................................................. 54 52 53 48 21 34 36 44 46 47 1 3 4 5 6 7 14 17

xiv 3.8 Femtosecond kinetics profiles of the transient absorption signal at various probe wavelengths for Zn()TPTBP in pyridine, excited at 640 nm ........... 3.9 Zn()TPTBP in pyridine; first lifetime/wavelength dependence.............................. 3.10 Normalized kinetic profiles of the transient absorption signal at 520 nm for Zn()TPTBP in benzonitrile and pyridine solutions after 640 nm excitation.................................................................................................................... 3.11 Nanosecond transient absorption difference spectra of Zn()TPTBP in Ar saturated pyridine_toluene solution at different delay times followed by 460 nm excitation....................................................................................................... 3.12 Nanosecond kinetic profile of the transient absorption signal in Ar saturated pyridine_toluene solution, exc= 460 nm .................................................................. 3.13 Kinetic diagram for the excited state deactivation of Zn()TPTBP ......................... 4.1 Side view of the DFT optimized molecular structure of M()TPTBP, M= Cu, Co ................................................................................................................. 4.2 Energy level diagram for Co-, Ni- and CuTPTBP. Orbital energies are obtained from spin-restricted calculations................................................................................ 4.3 4.4 4.5 Energy level scheme for Co()TPTBP together with contour plots of orbitals....... Energy level scheme for Cu()TPTBP together with contour plots of orbitals........ The energy level diagram obtained from spin unrestricted calculations for Co()TPTBP and Cu()TPTBP................................................................................ 4.6 4.7 The 23a1 orbital in Co()TPTBP and the 23b2 orbital Cu()TPTBP ....................... Normalized ground state absorption spectra of M()TPTBP complexes with M = Cu, Ni in toluene and Co in hexane ................................................................... 4.8 4.9 The theoretically predicted dark states lying below the Q state ................................ Transient absorption behavior of Co()TPTBP in hexane excited at 400 nm .......... 78 80 83 76 77 72 74 74 70 60 62 59 58 55 57

xv 4.10 Two time regimes of the transient absorption spectra of Co()TPTBP in hexane excited at 635 nm........................................................................................... 4.11 Kinetic profiles of the transient absorption signal at 500 nm and 680 nm probe wavelengths of Co()TPTBP in hexane after 635 nm excitation ............................. 4.12 Spectra recorded immediately after a laser pulse at 400 nm and at 3 ps later in Co(II)TPTBP in hexane ............................................................................................. 4.13 Temporal evolution of the transient absorption spectra of Cu()TPTBP in toluene (2.8 M), excited at 640 nm.......................................................................... 4.14 Evolution of the absorption spectra of Cu()TPTBP in benzonitrile, after excitation at 640 nm................................................................................................... 4.15 Time profiles of the transient absorption signal at two probe wavelengths for Cu()TPTBP in toluene after photoexcitation at 640 nm ......................................... 4.16 Normalized kinetic profiles of the transient absorption signal at 653 nm for Cu()TPTBP in two different solvents after 640 nm excitation ............................... 4.17 Proposed schematic diagrams for the excited state relaxation pathways of Co()TPTBP and Cu()TPTBP................................................................................ 5.1 Orbital energy levels for Cr and Mn porphyrin complexes with trivalent metal chlorides by iterative extended Hckel method......................................................... 101 5.2 Normalized ground state absorption of Cr()TPTBPCl in toluene, DMF and benzonitrile solutions................................................................................................. 102 5.3 Transient absorption spectra of Cr()TPTBPCl in Toluene, excited at 400 nm; Transient absorption spectra of Cr()TPTBPCl in DMF, excited at 640 nm .......... 103 5.4 Kinetic behavior of Cr()TPTBPCl in toluene at 530 nm after 640 nm excitation.................................................................................................................... 105 5.5 Transient absorption spectra of Cr()TPTBPCl in benzonitrile solution following 640 nm excitation ...................................................................................... 106 94 90 90 89 88 86 85 84

xvi 5.6 The kinetic profile of Cr()TPTBPCl in benzonitrile solution following 640 nm excitation.................................................................................................................... 106 5.7 5.8 Absorption spectra of Mn()TPTBPCl in toluene, benzonitrile and in DMF ......... 109 Transient absorption spectra of Mn()TPTBPCl in toluene solution following 400 nm excitation....................................................................................................... 111 5.9 Kinetic behavior of the Mn()TPTBPCl in toluene solution at 530 nm and 686 nm followed by 400 nm excitation............................................................... 112 5.10 The spectral cuts taken from early time and later times of spectral evolution of Mn()TPTBPCl in benzonitrile solution following 400 nm excitation................... 113 5.11 Femtosecond kinetic profiles of the transient absorption signals of Mn()TPTBPCl in benzonitrile solution after excited at 640 nm ........................... 114 5.12 Proposed schematic diagram for the excited state relaxation pathways of Cr()TPTBPCl and Mn()TPTBPCl ................................................................. 115 6.1 Top view and side view of the DFT-optimized molecular structure of Pt()TPTBP together with atom labeling.................................................................. 118 6.2 6.3 6.4 Energy level scheme for M()TPTBP, M= Ni, Pd, Pt .............................................. 124 Contour plots of the MOs of Pt()TPTBP ................................................................ 127 Ground state absorption of M()TPTBP (M= Pt and Zn) in toluene solution; extinction coefficients are given for absorbance data................................................ 129 6.5 Normalized room temperature absorption and fluorescence spectra and phosphorescence spectra in toluene solution ............................................................. 132 6.6 Evolution of the transient absorption spectra of Pt()TPTBP in toluene excited at 400 nm and 610 nm ............................................................................... 134 6.7 Kinetic profile of the Pt()TPTBP in toluene solution reported at 530 nm upon excitation at 400 nm; kinetic trace at 584 nm upon excitation at 610 nm ........ 135

xvii 6.8 Nanosecond transient absorption spectra of Pt()TPTBP in Ar-saturated toluene at different delay times followed by 430 nm excitation ............................................ 137 6.9 Nanosecond kinetic profiles of the transient absorption signals of Pt()TPTBP, excited at 430 nm ....................................................................................................... 138 6.10 Proposed excited state deactivation mechanism for Pt()TPTBP............................. 141

xviii LIST OF TABLES Page 1.1 Symmetry presentation of metal and porphyrin orbitals in metal porphyrinates ............................................................................................................. 3.1 Selected bond distances (Ao) and bond angles(deg) calculated for M()TPTBP in the D2d confirmation ........................................................................ 3.2 Vertical excitation energies (Eva) and oscillator strengths (f) computed for the lowest optically allowed excited states of Zn() and Ni()TPTBP.......................... 3.3 Excitation energies (eV) obtained for the low-lying excited states of Zn()TPTBP ............................................................................................................. 3.4 4.1 The photophysical properties of Zn()TPTBP.......................................................... Selected bond lengths () and bond angles (deg) calculated for MTPTBP in the saddled D2d conformation .......................................................................................... 4.2 Calculated vertical excitation energies (Eva) and oscillator strengths (f) for the optically allowed excited states of MTPTBP (M = Co(II), Ni(II), and Cu(II)) in the D2d confirmation and compared to experimental data ..................................... 4.3 Excitation Energies (eV), composition and character of the lowest excited states of Co()TPTBP ............................................................................................... 4.4 Excitation Energies (eV), composition and character of the lowest excited states of Cu()TPTBP ............................................................................................... 6.1 Comparison of the optimized theoretical values of the selected bond lengths (Ao) and bond angles (deg) with x-ray data for the Pt()TPTBP...................................... 122 6.2 Selected bond distance and bond angles calculated for MTPTBP, M=Pd, Pt, Ni ..... 123 82 81 80 79 51 61 49 45 15

xix 6.3 Vertical excitation energies and oscillator strengths (f) computed for the optically allowed excited states of M()TPTBP(M= Zn, Pt) responsible for the appearance of the Q band and B band and compared with experimental data .......... 130 6.4 Excitation energies (eV) calculated for the low-lying excited states of Pt()TPTBP ............................................................................................................... 131 6.5 6.6 Photophysical properties of M()TPTBP(M = Zn, Pd, Pt) ....................................... 133 Equilibrium derived triplet state energies for Pt and Zn complexes. Pt is in toluene solution and Zn in 1% pyridine-toluene solution...................................... 140

1 CHAPTER 1: INTRODUCTION Basic Photophysics The absorption of a photon creates excited states of the molecules that are unstable and the excess of energy will be dissipated in various routes as the molecule returns to its ground state. Figure 1.1 illustrates the Jablonski diagram1 that is useful compilation of the states and processes that may be involved when excited states deactivate to the ground state. The singlet ground state is depicted by the horizontal thick line labeled as S0 and higher singlet electronic states are represented as S1, S2 and Sn. Triplet states are labeled with T in a similar manner. Within each electronic state, vibrational energy states exist and are represented using thin lines. The absorption of light by ground state molecules are depicted by upward blue arrows. A molecule in its ground state can be excited to any number of singlet states (S1, S2). After excitation to S2, the molecule usually rapidly and non-radiatively relaxes to the lowest vibrational level of S1.

Sn S2 IC ISC ISC VR IC
Phosphorescenc

S1
Fluorescence

Ground state

S0
Figure 1.1. Jablonski diagram to depict the energy relationship and rate processes between electronic states.

VR

2 The vibrational cascade of S1 continues until there is a crossing between S1 and T1. In that crossing region an isothermal intersystem crossing process can occur resulting in population of the triplet state. Relaxation to the ground state takes place either radiatively (fluorescence and phosphorescence) or non-radiatively (internal conversion-IC and intersystem crossing-ISC). In fact, absorption and fluorescence are inverse processes. Fluorescence is the radiative transition between states of like multiplicity e.g.S1 S0. Phosphorescence is a radiative transition between states of unlike multiplicity e.g.T1 S0. Internal conversion (IC) is the radiationless transition between states of the same multiplicity (S2S1) and intersystem crossing process occurs when it occurs between the different spin states (S1T1). Vibrational relaxation is also a radiationless transition and it is from higher vibronic level to the lower one within the same electronic state.

Electronic structure of Metallotetrapyrroles Metal-Macrocycle interaction and UV-visible spectra Complexes with various tetrapyrrole ligands namely porphyrins and porphyrazines have attracted considerable interest because of diverse potential applications. Some porphyrins are naturally occurring and are involved in a wide variety of biological processes. Porphyrins consist of four pyrrolic units, linked together by four methine (=CH-) bridging groups. Figure 1.2 illustrates the different compounds derived from the basic structure of cyclic tetrapyrroles. Porphyrazines are synthetic porphyrins differ from porphyrins due to the presence of aza bridges (nitrogen atoms) instead of methine links.

3
N

NH

C C Cmeso

N N NH N

HN N N

HN

Porphyrin

Phthalocyanine

HN

HN

NH

NH

Tetrabenzoporphyrin

Tetraphenyltetrabenzoporphyrin

Figure 1.2. Structures of different types of tetrapyrrole macrocycles.

Phthalocyanines and naphthalocyanines also contain the basic structure of porphyrazines, but they differ by the presence of benzo rings fused to the pyrrole rings. Porphyrins are aromatic and they conform to the Hckel aromaticity condition in which 4n+2 electrons (n=5) are delocalized over the macrocycle. A porphyrin has eight positions and four meso- positions available for substitution. Porphine, the macrocycle having four pyrrole rings is the parent structural compound for porphyrins. Following removal of the two protons the four pyrrolic nitrogen atoms become equivalent and the compound can act as a tetradentate ligand for binding a variety of

4 metal ions. The cavity size of the macrocycle is such that most metal ions can be coordinated therein. Many of the resulting metalloporphyrins show important biological activities: as iron complexes in the hemoproteins, as magnesium complexes in the chlorophylls and as a cobalt complex in Vitamin B12.2 By varying the choice of the metal center, the bonding and characteristics of the metalloporphyrin may be critically affected. This diversity is one reason why metalloporphyrins have found many applications in modern life, such as magnetic materials,3,
4

photoconductive materials, non-linear optical materials5 and tumor photo-therapeutic

drugs.6 Metalloporphyrins (MPs) generally have high thermal stability and show strong electronic transitions in the visible and ultraviolet regions. Their electronic states deactivate on picosecond, nanosecond and millisecond time scales and a variety of intermediate states have been identified.7, 8 In order to evaluate the applications of MPs, it is necessary to understand the electronic structure and photophysical properties, particularly the mechanism of excited state deactivation.

Figure 1.3. Porphyrin HOMOs (bottom) and LUMOs(top); adapted from reference 9 Electron densities are shown in red and blue.

5 To interpret their various electronic states, optical absorption spectra and luminescence properties, Martin Gouterman first proposed a four-orbital model in the 1960s and it remains an effective model for explaining the absorption spectra of porphyrns.7 This model is depicted in Figure 1.3 and it illustrates the electronic density distributions in the orbitals. The a1u and a2u orbitals are HOMOs and the two LUMOs are identified as eg(*). As seen in the Figure 1.3, the HOMO a2u orbital is mainly localized on the pyrrolic nitrogen and meso- carbon atoms while HOMO-1 a1u has contribution mainly from the C and C atoms. The LUMOs are delocalized on the porphyrin ring. For a molecule with D4h symmetry, the eg(*) orbitals are strictly degenerate whereas the two a orbitals are nearly degenerate.10 The electronic configuration for porphyrin in the ground state is (a1u)2 (a2u)2 with 1A1g character.

dx2-y2 eg() d- -d d-d dxz dyz dxy a2u() Porphyrin a1u() Metal dz2

Figure 1.4. Schematic orbital diagram showing possible transitions of metalloporphyrin adapted from ref
11

6 Figure 1.4 describes the schematic diagram showing the possible transitions of metalloporphyrins. The absorption bands arise from transition between two HOMOs and two LUMOs (*). Accordingly the lowest singlet excited configurations are 1(a1u, eg) and
1

(a2u,eg) both having the Eu character. The Q bands are the result of the transition dipoles

nearly canceling each other out, resulting in a weaker absorption band. The higher energy B band transition results from a linear combination of the two transitions adding the transition dipoles and it is intense.11 In the free base porphyrins, the central protons lift the degeneracy of the eg orbitals causing the Q bands to split into Qx and Qy.10 Typical ground electronic state absorption spectrum of a metalloporphyrin is shown in Figure 1.5.
1.2

Soret or B band

1.0

Absorbance

0.8

0.6

0.4

0.2

Q bands
0.0 300 350 400 450 500 550 600

Wavelength/nm

Figure 1.5. A typical absorption spectrum of a metalloporphyrin.

The four orbital model has been very effective in explaining the effects of various substituents, central metal ions and extraneous ligands.10 As shown in Figure 1.3, MO calculations of the porphine core have shown that the a1u orbital has nodes at the pyrrole nitrogens and it cannot directly interact with metal. It also has nodes at the meso- carbons and is not expected to be influenced by meso substitution. In contrast, the a2u orbital should be strongly affected by meso substituents. On the other hand the a2u orbital puts less charge at

7 the carbons of the pyrrole rings than a1u orbital does. As a result the a1u level is shifted when compared to the pyrrole substituted porphyrins. Less electronegative metals shift a2u to higher energy and more electronegative metals stabilize a2u. Hypso porphyrins show blue shifts of the absorption spectra compared to regular porphyrins. If the metal possesses filled d orbitals, d electron donation from the dxz and dyz orbitals to the empty eg- *- orbitals of the porphyrin may occur, raising the eg * orbitals and lowering the d orbitals which have become bonding. (metal to ring back bonding, Figure 1.6). As a result the energy gap between the LUMO and HOMO will increase showing the hypsochromic shift.
eg

eg

dxz

dyz

dxy

a2u a1u Normal Hypso-Type Metal(d6)

Figure 1.6. Origin of the hypsochromic shift of the Q band. Taken from ref 12 Normally the replacement of a 3d metal ion by one having 4d or 5d orbitals gradually enhances back-bonding because the 4d or 5d orbitals have a larger radial expansion and thus penetrate the antibonding orbitals more. Indeed a large increase in the hypsochromic shift of the Q band in the series Ni < Pd < Pt can be seen indicating the increase in metalto- porphyrin back-donation. Hyper absorption spectra show extra absorption bands in addition to Q and B bands.

8 Metallotetrapyrroles: Background Metallo-tetraphenyltetrabenzoporphyrins (MTPTBPs) are an interesting class of tetrapyrrole chromophores because of the extension of the -system and meso-substitution. In these porphyrins, a combination of electronic and structural factors, such as extension of the -system, meso-substitution and highly distorted macrocycle core causes a red-shift and intensification of the Q band absorption as compared to other MPs13 making these complexes potentially useful in diverse practical applications. One such application is photothermal therapy (PTT), which is a promising approach to tumor treatment.8, 14 In addition to having a high molar decadic extinction coefficient in the red spectral region, where light penetration of tissue is optimal, efficient photothermal sensitizers for PTT should also show fast radiationless decay of the excited states, converting the photon energy into vibrational energy of the ground state, thereby initiating thermal events that can be lethal to the cell. The ability of a compound to photothermally destroy cancer cells depends on how rapidly the initial photo-produced excited state deactivates to the ground state surface. This, in turn, depends on the nature and the lifetime of the electronic states lying between S1 and the ground state -the so-called silent states. The energy and nature of these states are critically dependent on the central metal. Metallotetrapyrroles with first row transition metal centers (e.g. Co, Fe, Ni, Cu) have been shown to undergo fast radiationless deactivation of their excited states because the metal incorporated into the macrocycle cavity introduces a manifold of electronic states with metalcentered and/or metal+system character, some of which can be situated at lower energy than the pure ,* states that are populated by a photo-excitation process.15 These low-lying states may provide rapid non-radiative channels for excited state deactivation, which is an optimum situation for PTT.

9 The effect of the central metal on the photophysical properties of MPs, especially the Ni(II) variants, has been investigated intensively.10, 16-34 The results of extended Hckel calculations and the lack of luminescence supported the idea that the normally emissive
1,3

(,*) excited states of the porphyrin ring deactivate rapidly through low-lying metal

centered 1,3(dz2,dx2-y2) states.7, 16 Holten and et al showed that in nickel porphyrins such as Ni(II)OEP and Ni(II)TPP, the (d,d) state forms within <1 ps, followed by deactivation to the ground state in 200-500 ps.28-30, 35 In porphyrins with Zn(II) centers where the metal has a d10 electronic configuration, the interactions between the porphyrin -orbitals and the metal are negligibly small.6 The deactivation of Zn(II)P singlet state S1 occurs largely through the T1 triplet state with some raditive process. The quantum yield of triplet state for Zn(II)TMPyP was found to be 0.98 and for Zn(II)TPPS and Zn(II)TPP, it was 0.96.36 The triplet state deactivates with the lifetime of 1.3 ms for Zn(II)TMPyP, 1.4 ms for Zn(II)TPPS and 1.2 ms for Zn(II)TPP.36 The phosphorescence quantum yields for these compounds are <10-4 at 298 K due to efficient non-radiative relaxation of the triplet state. Chen and et al33 have investigated the transient spectra and kinetics of different benzoporphyrin derivatives including Zn(II)TPTBP in benzene solution by means of transient spectroscopy with ca. 35 ps resolution and pointed out that ZnTPTBP exhibited both 1(,*) and 3(,*) transitions. Rogers and et al8 also investigated meso tetraphenylmetalloporphyrins, using TDDFT calculations and nanosecond flash photolysis and characterized the T1Tn absorption spectra and fluorescence quantum efficiencies. The fact that Co(II), d7, and Cu(II), d9, are paramagnetic introduces complications to the excited state picture. The unpaired d electron interacts with the macrocycle orbitals generating doublet multiplicity in the ground and , excited states, and splitting the triplet states to trip-doublet (2T1) and trip-quartet (4T1) states that lie very close in energy.13 High

10 time resolution studies on various Cu porphyrins have shown that intersystem crossing from the primary excited 2S1 state into the triplet manifold occurs in less than 350 fs and the main cause for the ground state repopulation involves an equilibrium set of triplet states
2

T1(,*)/4T1(,*).29, 37 Calculations showed that in Cu complexes the half-filled dx2-y2

orbital lies within the HOMO-LUMO gap giving rise to many charge transfer transitions.38 Observations suggest that a CT state lies close in energy above the 2T and 4T in noncoordinating solvents and that a non-luminescent CT state is thermally accessible.15 Several ultrafast transient absorption experiments and extended Hckel calculations predicted that a low-lying charge transfer state a2u() Co(dz2) participates in the deactivation process in Co() porphyrins such as octaethyl and tetraphenyl complexes.32, 34 Determination of d-orbital energies of low lying excited states from ESR data on Co(II) porphyrins suggest that up to seven possible metal centered (d,d) states may lie below 1.24 eV, which is well below the 2T1( ,*) state and the lowest lying (,d) charge transfer state.38 These possibly participate in the deactivation process.32 Chromium() and Manganese() porphyrin complexes are interesting compounds mainly because of their unique absorption spectra due to the unusual electronic structure induced by half-filled metal d orbitals. Irvine et al.39, 40 who used 1-ps excitation at 597 nm to examine Mn()TPPCl in CH2Cl2 and pyridine, reported that the lifetime for the decay of the strongly absorbing species near 500 nm was 17 ps and assigned to the decay of a ring (,*) tripmultiplet state. Holten et al41 reported the excited state kinetics at 500-900 nm of Mn()TPPCl and Mn()OEPCl in CH2Cl2 and pyridine and reported two transients having fast and slower components. The fast decay had 5-30 ps lifetime and the slower components had an 80 ps lifetime for TPP and 140 ps lifetime for OEP and they assigned the short-lived component to the tripquintet 5T1(,*), a fraction of which relaxes to the longer lived

11 trpseptet, 7T1(,*). And also they suggested that decay of both tripmultiplets possibly proceeds via lower energy CT or d,d excited states. Gouterman et al. reported that there were two luminescence bands at 815 nm and 850 nm from ClCr()TPP at 77 K, and those bands were assigned to the emission originated from tripquartet 4T(,*) and tripsextet 6T(,*) states.42 And also they showed that the emissions from the quartet and sextets were in thermal equilibrium. Photophysical studies on Cr porphyrins were carried out to elucidate the photodissociation mechanism of the axial ligand. Hoshino et al.43, 44 reported laser flash photolysis of ClCr()TPP(L) (L= sixth axial ligand) in various solvents and suggested that 4S1(,*) excited state acts as the main route for the photodissociation process. Jeoung et al.45 found out that the temporal evolutions of photoinduced absorption and bleaching signals of XCr()TPP(X= Cl, Br) in benzene exhibit biphasic decay profiles with time constants 1 and 20 ms. The faster decay was assigned to the four coordinated CrTPP* species and the slower decay component to the recombination process returning to the original five-coordinate XCr()TPP species. A significant reduction in the lifetime of photoexcited ClCr()TPP in THF was observed as compared with that in benzene. An investigation on the luminescent properties of Cr() porphyrins showed that the lifetime of the photexcited state is relatively short ~295 ps in ethanol and also depends on the solvent.46 The photophysical properties of the second and third row transition metal tetrapyrrole complexes (Ru, Pd, Pt, etc) differ greatly from the first row metals showing intense phosphorescence and long lived triplet T1 state localized on the system.10, 27 The effects of heavy metals on spectroscopic properties have been attributed to the spin-orbit interaction that raises the energy of the unoccupied d orbitals. Coordination of a heavy metal atom into the system increases the rate of the intersystem crossing between singlet and triplet states of the metalloporphyrins, thereby enhancing the rate of radiative decay. For example, Pd()

12 porphyrins show a weak fluorescence (F< 10-4) 47 and in Pt complexes only delayed fluorescence could be observed.10 The research presented in this dissertation is focused on an investigation of the photophysical properties of the metallotetrabenzoporphyrins with first row transition metals Cr(), Mn(), Co(), Cu(), Zn(), and the third row Pt(), analogue. The effect of the different central metal on the electronic properties and the excited state dynamics of tetrabenzoporphyrins are discussed from both experimental and theoretical points of view. Theoretical-only investigations of Ni() and Pd() analogues have been performed to give a full picture about the nature of the deactivation mechanism. The first two chapters discuss some of the aspects of photophysics and tetrapyrrole molecules together with the methods and materials used in the experiments and calculations. Chapter 3 describes the ground and excited state properties of Zn()TPTBP using a combination of DFT/TDDFT and transient absorption spectrometry in order to provide experimental and theoretical evidence on the spectral properties of the -localized singlet and triplet states of the tetraphenyltetrabenzoporhyrin macrocycle. The results are compared to Ni()TPTBP. Accumulated experimental and theoretical evidence on the excited state deactivation of Cu(II)TPTBP and Co(II)TPTBP complexes are described in chapter 4. In chapter 5, the photophysics of Cr()TPTBPCl and Mn()TPTBPCl are described using transient absorption spectrometry to provide data necessary in understanding the influences that metals with partially occupied d orbitals have on the photophysical properties of the porphyrin macrocycle. Chapter 6 is introduced to describe the heavy metal effect on the photophysics of tetrabenzoporphyrins. The experimental results from femtosecond and nanosecond transient absorption studies have combined with relativistic DFT and TDDFT calculations to see the effect of heavy metals on photodeactivation. Only calculations were performed with Pd()TPTBP and compared the metal influence on the Ni Pd Pt in transition series.

13 Bond-Type in metalloporphyrins On chelating with a metal ion the porphyrin nucleus loses two protons from its pyrrole nitrogen atoms. Thus the chelating species is a di-anion and electrostatic forces undoubtedly contribute to the binding.48 When porphyrin is coordinated to a metal as a tetradentate ligand there are four six-membered chelate rings with delocalized bonds, hence, there are additional rings with delocalized -systems. The most important geometrical type in porphyrins is the square planar tetracoordinate porphyrin chelate with D4h symmetry having low spin state.49 Squarepyramidal penta-coordinate complexes are formed when a further ligand is added perpendicularly on one side of the porphyrin plane. The further addition of another out-of plane ligand results in octahedral complexes and become high spin due to the electronic rearrangement being forced by the increasing energy of the dz2 orbital induced by the axial ligation.50 Among the five d orbitals in metal porphyrins, the dx2-y2 orbital lies along the x and y axes pointing towards the four nitrogen atoms and the dz2 orbital lies along the molecular fourfold symmetry z axis, perpendicular to the plane. In the plane, the dxy orbital lies transecting the dx2-y2 orbital, and the dxz and dyz orbitals lie between the xz and yz axes respectively. If the dx2-y2 and dz2 orbitals are not filled with electrons, unpaired electrons may be transferred to the ligands through different types of metal-ligand bonding interactions such as ligand-to-metal donation, ligand to metal donation and metal- to- ligand back bonding.51 The spatial disposition of the dxy, dxz and dyz orbitals means that they do not play a part in bonding with ligands, but they can overlap with vacant orbitals to form bonding. In the square planar porphyrin chelates the dxz and dyz orbitals of the metal ion are sterically able to overlap with vacant p orbitals of the ring nitrogen atoms of the porphyrin whereas in square pyramidal or octahedral complexes the dxz and dyz orbitals of the metal ion can overlap with vacant orbitals in the fifth and sixth positions.48 For four and six coordinate

14 metalloporphyrins with D4h symmetry, the dx2-y2 orbital interacts with porphyrin type molecular orbitals with nodal planes passing through meso-carbons. The dz2 orbital has electron density along the z axis and will interact mostly with axial ligand orbitals of symmetry.52 Figure 1.7 illustrates these orbital types.

Figure 1.7. d metal orbitals in porphyrins, taken from ref 52

Symmetry in Metalloporphyrins Many porphyrins that are important in biological applications are observed to be nonplanar. Non-planar distortion may be caused by peripheral steric crowding, electronic interactions involving axial ligands, crystal packing effects, the size of the central ion and specific metal-ligand orbital interaction.53 For a planar metalloporphyrin with D4h symmetry the a1u and a2u HOMOs are orthogonal to each of the five metal d orbitals. With a ruffling deformation introduced, the symmetry of a six coordinate metalloporphyrin will be lowered from D4h to D2d ; both dxy and a2u orbitals will be of b2 representation making it symmetry-allowed and can therefore interact.54 Saddling makes the metal dx2-y2 and porphyrin b2 orbital interaction while a five-coordinate metalloporphyrin with C4v symmetry, both dz2 and a2u will be in a1 representation to interact.

15 Orbitals D4h planar metal dx2-y2 dz2 d dxy porphyrin LUMO HOMO b1g a1g eg b2g eg a1u a2u D2h ag ag b2g, b3g b1g b2g, b3g au b1u Point Group D2d ruffled b1 a1 e b2 eg b1 b2

saddled b2 a1 e b1 eg b1 b2

C4v domed b1 a1 E b2 a2 a1

C2v a1 a1 b2,b1 a2 a2 b1

Cs a a a a a a a

Table 1.1. Symmetry presentation of metal and porphyrin orbitals in metal porphyrinates, adapted from ref 52, 54, 55

Excited states of porphyrins and characterization of excited states of porphyrins Transient absorption measurements allow measuring the difference in absorption spectra between an excited state and the ground state. Those absorption difference spectra such as ,*, d-d, CT (, d) or d, * appear to have distinct features that can be used to identify them and they are most important in explaining their photophysical and photochemical behavior.

,* state of the ring Both singlet and triplet ,* spectra contain a broad absorption extending from 500 nm throughout the near infrared. The 1(,*) spectra could also display a characteristic Q band stimulated emission which appears as a negative feature to the red of the Q band bleaching. The position of Q(0,1) stimulated emission coincides with the position of Q(0,1) spontaneous emission.(fluorescence). Therefore, stimulated emission occurs in the vicinity of 650 nm for the metalloporphyrins and near 700 nm for the free-base complexes.29 The triplet

16
3

(,*) spectrum is marked by a distinct near-infrared absorption peak and always appears at

the long wavelength edge of the absorption.

d,d ligand field states The absorption spectra of low-lying d,d excited states of metalloporphyrins appear to be similar to but red shifted from the ground state spectra. Picosecond studies on Ni16-21 and Co32 porphyrins have shown absorption difference spectra in the visible and the Soret region that have 15-20 nm to the red of ground state bleachings. d,d state states can be thought of as a combination of porphyrin ground state -system with an electronically excited metal center. The optical absorption spectrum of such an entity will be dominated by the Soret and Q bands of the ring and it will differ from the original ground state spectrum slightly because of the electronic effects imparted by the changed configuration of the d-electrons. In general, the spectrum of metalloporphyrin d,d state exhibits derivative shaped absorption changes. In general, one expects the spectrum of metalloporphyrin d,d state to exhibit derivative shaped absorption changes since the porphyrin system has returned to its ground state electronic configuration. Thus, the absorption spectrum of d,d state should be dominated by the same * transitions governing the spectrum of the ground electronic state of the complex but shifted in energy and possibly intensity due to the new metal electronic configuration.56

(,d) and (d, *) metal ring CT states Low lying charge transfer states are also formed by radiationless deactivation of higher energy excited states. Accordingly the energies of these CT states and their transient behavior are expected to be dependent on the electronic properties of the ring, the central metal ion and the axial ligands.10 These CT excited states should show little difference to

17 those observed upon production of metalloporphyrin ring * transitions since the most of the oscillator strength for these excited states come from the porphyrin ring.57

Use of tetrapyrrolic photosensitizers for cancer treatment Metallo-tetrapyrroles are potential candidates for diverse applications due to the inherent chemical flexibility of the metallomacrocycle that allows modulation of their physico-chemical properties through ligand and metal modification. Among them, a significant use of these types of molecules is in the area of cancer treatment. Different types of therapeutic modalities are available and here, photodynamic therapy (PDT) and photothermal therapy (PTT) will be discussed in detail. With these kinds of treatments, a non-toxic photosensitizing agent will be injected to the targeted tissue and followed by the specific irradiation using selected visible or near IR light, usually from a laser. The sensitizing agents should accumulate and be retained primarily in the tumor cells rather than in healthy tissue.58 The mechanism of PDT is described in Figure 1.8. There, light, O2 and a photosensitizing drug are combined to produce a selective therapeutic effect.

Photosensitizer (excited state)

Tissue oxygen

Free radicals, singlet

Light

Photosensitizer (ground state)

Cellular toxicity

Figure 1.8. Mechanism of action of PDT modified from ref. 59

18 PDT is based on the concept that certain photosensitizers can be localized in neoplastic tissue and subsequently they can be activated with the appropriate wavelength (energy) of light to generate active molecular species such as free radicals and singlet oxygen (1O2) that are toxic to cells and tissues.14, 59-62 In general, photosensitizers with longer absorbing wavelengths and higher molar absorption coefficients at these wavelengths are more effective photodynamic agents. The photophysical process involved in PDT can be described as follows. The ground state electronic state of the photosensitizer is a singlet state (S0) and upon excitation at the appropriate wavelength, it is excited to the short-lived first excited singlet state (S1).The photosensitizer can return to the S0 state by emitting the absorbed energy as fluorescence or by internal conversion. Alternatively the S1 state can convert to the first excited triplet state (T1) by intersystem crossing. The T1 state is sufficiently long-lived to take part in chemical reactions and therefore photodynamic action is mostly mediated by the T1 state. When the photosensitizer returns to the ground state it can generate a manifold concentration of reactive intermediates as a result of an oxidation of biomolecules in the cell. There are two types of photodynamic reactions.63 Type photoprocess are electron or hydrogen transfer reactions between the T1 photosensitizer and target molecules generating reactive intermediates which are harmful to cells such as superoxide, hydroperoxyl and hydroxyl radicals. The type photoprocess is an electron spin exchange between the T1 photosensitizer and 3O2. It produces the first excited-singlet state of oxygen (O21g ) which is regarded as the main mediator of phototoxicity while the photosensitizer returns to S0 state. A good photosensitizing agent should not be toxic in the absence of light and should be localized in the target tissue as selectively as possible and be eliminated from the body quickly to avoid generalized skin photosensitization.60

19 PDT is a binary modality for tumor treatment which requires the presence of two independent substituents to initiate the treatment process. On the other hand Photothermal therapy (PTT) process only requires the presence of photosensitizer alone. A potential advantage of PTT over PDT is the lack of need of the presence of oxygen in the irradiated tissue and the lack of the necessity that the irradiating photon has sufficient energy to generate singlet oxygen.14 For a compound to be an effective photothermal agent, it should be able to very rapidly return to its ground state after photoexcitation, generating a vibrationally hot ground state molecule. Therefore the most useful photosensitizers for PTT would be chromophores with excited electronic states that only decay non-radiatively to the ground state converting the photon energy into the thermal event. Following the proposal of PTT for tumor treatment, tetrapyrroles with first row transition metal centers have attracted much attention due to their high extinction coefficient in the near IR region where light penetrates into tissues more effectively, their high photostability and the short lifetime of the excited states allowing for the generation of high local temperatures. Metallotetrapyrroles with first row transition metal centers have been shown to undergo fast radiationless deactivation of their excited states since the metal incorporated into the macrocycle cavity introduces a manifold of electronic states with metalcentered and/or metal+system character, some of which can be situated at lower energy than the pure ,* states that are populated by a photo-excitation process.15 These low-lying states provide rapid non-radiative channels for the excited state deactivation, which is an optimum situation for PTT. Here, the excited state dynamics of Metallotetraphenyltetrabenzoporphyrins (MTPTBPs) have been studied with the intent to formulate an understanding of how such dynamics depend on molecular characteristics to explore the ability of these kinds of molecules to be used as photothermal agent for future.

20 The effect of the extension of porphyrin ring and meso-phenyl substitution This study is all about tetraphenyltetrabenzoporphyrins and it is fruitful to compare how these molecules deviate from the unsubstituted porphyrins. To know the structure property relationship, it is important to understand how chemical changes affect the photophysical properties. Extension of the porphyrin ring by benzo-annulation results in red shifts in both the ground (Q and B bands) and triplet excited state (T1-Tn) absorption spectra.13 Rosa et al investigated the effect of benzo-annulation in Ni tetrapyrroles and found that NiTBP showed enhanced oscillator strength and significant red shift of the Q band compared to regular porphyrins.64 The red shifts of the ground state spectra may be due to some extent to the conformational changes as well as electronic effects due to the increased conjugation.65-69 Rogers and et. al have studied the difference in energy (E) relative to the planar porphyrin with extended macrocycle and meso substituted porphyrins to have an idea about the overall contribution of each type of substitution. The data showed that a large percentage of the red shifts observed is due to electronic effects which results from increased conjugation from the added benzo groups.13 There is significant separation in energy between the Gouterman HOMO and HOMO1 orbitals that are nearly degenerate in unsubstituted porphyrins64,70, 71 It has been shown that different substituents at the meso-carbon or at the periphery of the porphyrin core can alter the position of these orbitals, removing degeneracy to some extent, and thus giving rise to intensification and/or shifting of the Q band.13, 64, 68 As seen in Figure 1.3, the HOMO a2u orbital is mainly localized on the pyrrolic nitrogen and meso- carbon atoms while HOMO-1 a1u has contribution mainly from the C and C atoms. To selectively red shift the B band, an addition of conjugated groups at the meso-

21 position should be made and to selectively red-shift the Q band the addition of conjugated groups to the position should be made and the end result will be lowering the energy. The near degeneracy of the G-HOMO and G-HOMO-1 that exists in porphyrins does not occur in benzoporphyrin derivatives since the electronic effect of benzo-annulation partially removes the mixing of the Gouterman one-electron transitions.15, 64, 71 This makes the cancellation of the transition dipole moments in the Q band less effective, resulting in the enhanced oscillator strength of the Q band.

Effect of saddling Saddling is effected by the simultaneous tilting upward of two opposite pyrrole rings and the tilting downward of the two other opposite pyrrole rings. Figure 1.9 presents a schematic diagram to show the tilting of pyrrole rings and the plane of the drawing is the plane perpendicular to the porphyrin plane.

Pyrrole

N N

M
N N

Pyrrole

Cmeso

Figure 1.9. Definition of rotation angle of the phenyl plane between an upward tilted pyrrole and a downward tilted pyrrole from ref.64

The degree of saddling projections can be defined as the saddling angle that pyrrole rings makes with the porphyrin plane. The rotation of meso phenyl rings is described by the

22 angle between the phenyl plane and the porphyrin plane. Saddled meso-aryl porphyrins shows a quite acute aryl-porphyrin dihedral angles < 600 72. Rosa and et al reported that the saddling distortion of the porphyrin core and the tilting of the meso-aryl groups are coupled through a synergic mechanism that is entirely governed by intrinsic electronic factors.64 Calculation have showed that the energy of HOMO increases with increasing the number of phenyl groups while the change of LUMO is irregular. Detailed analysis has further indicated that the sequential decreasing of the HOMO-LUMO gap going from H2P to H2TPP with increasing phenyl numbers.73

DFT/TDDFT Methods: Background Density Functional Theory (DFT) has become a major tool to predict and rationalize the nature of the electronic ground state of transition metal compounds. The basic notion in DFT is that the energy of an electronic system can be expressed as a function of its electron density. The formal proof that the energy of an N- electron system can be defined without any approximation as a function of its density (r) was given in 1964 by Hohenberg and Kohn74. Thus DFT is an exact reformulation of the Schrdinger equation based on the HohenbergKohn theorem according to which the ground state energy of an electronic system is uniquely determined by the electronic density (r). DFT differs from Hartree-Fock ab initio methods in that it uses the electronic density rather than one electron wave functions. DF theory is turned into practical application after the Kohn-Sham (KS) theory75 was developed. The general DFT energy can be expressed as

E( ) = [TS ] + [VN ] + [VC ] + EXC ( )

where is the electronic density.

[TS ]

is the kinetic energy of the non-interacting electrons with the density of

23

[VN ] is the interaction energy of the external potential VN with

[ VN ] = VN ( 1) ( 1)dr 1

[VC ]

is the Coulomb energy due to the interaction between two charge distributions of (1)

and (2)

[VC] =

1 ( 1) ( 2 ) dr 1dr 2 r 12 2

EXC ( ) , is the exchange-correlation energy term and its exact functional dependence on is
unknown. To use DF theory effectively the exchange-correlation part has to be approximated. To find an accurate EXC ( ) continues to be great challenge in density functional theory. The simplest and widely used approximation is Local Density Approximation(LDA)76 which uses the homogeneous electron gas formula for the exchange and correlation energy, EXC which is written as EC ( ) = ( 1) C ( )dr 1 where C is the correlation energy per electron in a homogeneous gas. The most successful and widely used analytical expressions of c() is developed by Vosko, Wilk and Nusair (VWN)77. Recently, LDA and VWN have become synonyms in the literature78. Slater neglects the correlation energy and the exchange functional term is given as

EX ( ) = 3

3 1 1 ( 1) 8 3 3

and now is known as the Hartree-Fock-Slater or X method. More sophisticated approximations to the exchange-correlation energy incorporate non-local corrections, in which the exchange and correlation were improved by non-local gradient correction, due to Becke79 for the exchange and Perdew80 for correlation. Time dependent density functional theory(TDDFT) is popular for predicting excited state and response properties of molecules and is based on a Runge- Gross theorem, the time

24 dependent analog of the Hohenberg-Kohn theorem,81 which is a simple consequence of the time-dependent Schrdinger equation. All the DFT/TDDFT calculations performed here used the ADF (Amsterdam Density Functional) suite of programs together with BP functional and the ADF largest available 3STO basis set. The BP functional has provided accurate results for transition metal systems to predict the positions of the metal-based molecular orbitals relative to the ring orbitals and in describing pure valence excitations.82 The combination of DFT and TDDFT is capable of reaching accuracies ~ 100 meV in energy calculations. The combination of TDDFT and transient spectroscopy methods is becoming a promising strategy for excited state structure elucidation in larger molecular systems containing metals.

Glossary of acronyms

OEP = octaethylporphyrin TPP = tetraphenylporphyrin TMPyP = tetrakis(N-methylpyridyl)porphyrin TPPS=tetrakis(sulfonatophenyl)porphyrin

References

1. 2. 3. 4.

Jablonski, A. Z. Phys. 1935, 38. Milgron, L. R., The colours of life. Oxford University Press Inc., New York: 1997. Harutyunyan, A. R. Chem. Phys. Lett. 1995, 246, 615. Harutyunyan, A. R.; Kuznetsov, A. A.; Szymczak, H.; Szymczak, R.; Baran, M.;

Nabialek, A. J. Magnetism and Magnetic Materials 1996, 162, 338.

25 5. 2019. 6. Leznoff, C. C.; Lever, A. B. P., In Phthalocyanines: Properties and Applications. Gasstevens, M. K.; Samoc, M.; Pfleger, J.; Prasad, P. N. J. Chem. Phys. 1990, 92,

VCH Publishers: NewYork: Vol. Vol. 1989 (Vol. I), 1993 (Vols. II & III), 1996 (Vol. IV). 7. 8. 9. 10. Gouterman, M., The Porphyrins. Academic Press:New York: 1978; Vol. 3, p 1. Soncin, M.; Busetti, A.; Fusi, F. Photochem. Photobiol. 1999, 69, 708. Weaver, J. J. PhD Thesis, California Institute of Technology, 2005. Kalyanasundaram, K., Photochemistry of Polypyridine and Porphirin Complexes.

Academic Press: London: 1992. 11. 12. Suslick, K. S.; Watson, R. A. New. J. Chem 1992, 16, 633. Buchler, J. W.; Kokisch, W.; Smith, P. D., Springer Berlin / Heidelberg: 1978; Vol.

34, p 79. 13. Rogers, J. E.; Nguyen, K. A.; Hufnagle, D. C.; McLean, D. G.; Su, W.; Gossett, K.

M.; Burke, A. R.; Vinogradov, S. A.; Pachter, R.; Fleitz, P. A. J. Phys. Chem. A 2003, 107, 11331. 14. Camerin, M.; Rello, S.; Villanueva, A.; Ping, X.; Kenney, M. E.; Rodgers, M. A. J.;

Jori, G. Eur. J. Cancer 2005, 41, 1203. 15. Zamyatin, A. V.; Soldatova, A. V.; Rodgers, M. A. J., Inog. Chim. Acta 2006, 360,

(3), 857. 16. 17. Antipas, A.; Gouterman, M. J. Am. Chem. Soc. 1983, 105, 4896. Drain, C. M.; Gentemann, S.; Roberts, J. A.; Nelson, N. Y.; Medforth, C. J.; Jia, S.;

Simpson, M. C.; Smith, K. M.; Fajer, J.; Shelnutt, J. A.; Holten, D. J. Am. Chem. Soc. 1998,
120, 3781.

18.

Eom, H. S.; Jeoung, S. C.; Kim, D.; Ha, J.-H.; Kim, Y.-R. J. Phys. Chem. A 1997,

101, 3661.

26 19. Fournier, M.; Pepin, C.; Houde, D.; Ouellet, R.; VanLier, J. E. Photochem. Photobiol.

Sci. 2004, 3, 120.

20. 4015. 21. 22.

Kim, D.; Holten, D.; Gouterman, M.; Buchler, J. W. J. Am. Chem. Soc. 1984, 106,

Liao, M.-S.; Scheiner, S. J. Chem. Phys. 2002, 117, 205. Loppnow, G. R.; Melamed, D.; Leheny, A. R.; Hamilton, A. D.; Spiro, T. G. J. Phys.

Chem. 1993, 97, 8969.

23. 24. 25.

Nikolaitchik, A. V.; Korth, O.; Rodgers, M. A. J. J. Phys. Chem. A 1999, 103, 7587. Nikolaitchik, A. V.; Rodgers, M. A. J. J. Phys. Chem. A 1999, 103, 7597. Retsek, J. L.; Drain, C. M.; Kirmaier, C.; Nurco, D. J.; Medforth, C. J.; Smith, K. M.;

Sazanovich, I. V.; Chirvony, V. S.; Fajer, J.; Holten, D. J. Am. Chem. Soc. 2003, 125, 9787. 26. Rihter, B. D.; Kenney, M. E.; Ford, W. E.; Rodgers, M. A. J. J. Am. Chem. Soc. 1990,

112, 8064.

27.

Rihter, B. D.; Kenney, M. E.; Ford, W. E.; Rodgers, M. A. J. J. Am. Chem. Soc. 1993,

115, 8146.

28. 29. 30. 31. 32. 33. 34.

Rodriguez, J.; Holten, D. J. Chem. Phys. 1989, 91, 3525. Rodriguez, J.; Kirmaier, C.; Holten, D. J. Am. Chem. Soc. 1989, 111, 6500. Rodriguez, J.; Kirmaier, C.; Holten, D. J. Chem. Phys. 1994, 9, 6020. Sayer, P.; Gouterman, M.; Connell, C. R. Acc. Chem. Res. 1982, 15, 73. Tait, C. D.; Holten, D.; Gouterman, M. J. Am. Chem. Soc. 1984, 106, 6653. Vincett, P. S.; Voigt, E. M.; Rieckhoff, K. E. J. Chem. Phys. 1971, 55, 4131. Yu, H. Z.; Baskin, J. S.; Steiger, B.; Wan, C. Z.; Anson, F. C.; Zewail, A. H. Chem.

Phys. Lett. 1998, 293, 1.

35. 36.

Rodriguez, J.; Kirmaier, C.; Holten, D. J. Chem.Phys. 1991, 94, 6020. Kalyanasundaram, K.; Neumann - Spallart, M. J. Am. Chem. Soc. 1982, 86, 5163.

27 37. 38. Jeoung, S. C.; Takeuchi, S.; Tahara, T.; Kim, D. Chem. Phys. Lett 1999, 309, 369. Antipas, A.; Dolphin, D.; Gouterman, M.; Johnson, E. C. J. Am. Chem. Soc 1978,

100, 7705.

39.

Irvine, M. P.; Harrison, R. J.; Strahand, M. A.; Beddard, G. S. Ber. Bunsenges. Phys.

Chem 1985, 89, 226.

40. 41. 42. 2343. 43.

Chirvonyl, V. S.; Dzhagarov, B. M. Fuusika Mat. 1982, 31, 129. Kim, D.; Holten, D.; Gouterman, M. J. Am. Chem. Soc. 1984, 106, 2793. Gouterman, M.; Hanson, L. K.; Khalil, G. E.; Leenstra, R. J. Chem. Phys 1975, 62,

Hoshino, M.; Nagamori, T.; Seki, H.; Chihara, T.; Tase, T.; Wakatsuki, Y.; Inamo, M.

J. Phys. Chem. A. 1998, 102, (8), 1297.

44. 45. 46. 47.

Hoshino, M.; Tezuka, N.; Inamo, M. J. Phys. Chem. A 1996, 100, (2), 627. Jeoung, S. C.; Kim, D.; Cho, D. W. J. Raman Spectrosc. 2000, 31, 319. Harriman, A. J. Chem. Soc., Faraday Trans. 1982, 1, (78), 2727. Callis, J. B.; Gouterman, M.; Jones, Y. M.; Henderson, B. H. J. J. Mol. Spectrosc.

1971, 29, 410.

48.

Falk, J. E., Porphyrins and Metalloporphyrins. Elsevier Publishing Company: New

York: 1964; Vol. 2. 49. 50. 51. 52. McClure, D. S. Radiation Research 1960, 2, 218. Kim, D.; Oliver Su, Y.; Spiro, T. G. Inorg. Chem. 1986, 25, (22), 3988. Harutyunyan, A. R. Chem. Phys. Lett. 1995, 241, 168. Cheng, R. J.; Chen, P. Y.; Lovell, T.; Liu, T.; Noodleman, L.; Case, D. A. J. Am.

Chem. Soc. 2003, 125, (22), 6774.

53.

Tangen, E. PhD Thesis, University of Tromso, Tromso, Norway, 2003.

28 54. Ohgo, Y.; Hoshino, A.; Okamura, T.; Uekusa, H.; Hashizume, D.; Ikezaki, A.;

Nakamura, M. Inorg. Chem. 2007, 46, (20), 8193. 55. 56. Conradie, J.; Ghosh, A. J. Phys. Chem. B. 2003, 107, (26), 6486. Drain, C. M.; Kirmaier, C.; Medforth, C. J.; Nurco, D. J.; Smith, K. M.; Holten, D. J.

Phys. Chem. A 1996, 100, 11984.

57.

Holten, D.; Gouterman, M., In Optical Properties and Structure of Tetrapyrroles,

Blauer, G.; Sund, H., Eds. Walter de Gruyter, New York: 1985. 58. Bucking, M.; Dickson, E. F. G.; Farahani, M.; Fischer, F.; Holmes, D.; Jori, G.;

Kennedy, J. C.; Kenney, M. E.; Peng, X.; Pottier, R. H.; Weagle, G. Photochem. Photobiol.
B: Biol. 2000, 58, 87.

59.

Dolmans, D. E. J. G. J.; Fukumura, D.; Jain, R. K. Nature Reviews Cancer 2003, 3,

(5), 380. 60. 61. Nyman, E. S.; Hynninen, P. H. Photochem. Photobiol. B: Biol. 2004, 73, 1. Schmitt, F.; Govindaswamy, P.; Fink, G. S.; Ang, W. H.; Dyson, P. J.; Jeanneret, L.

J.; Therrien, B. J. Med. Chem. 2008, 51, (6), 1811. 62. 187. 63. 64. Foote, C. S. photochem. Photobiol. 1991, 54, 659. Rosa, A.; Ricciardi, G.; Barends, E. J.; Gisbergen, S. J. A. v. J. Phys. Chem. A 2001, Tedesco, A. C.; Rotta, J. C. G.; Lunardi, C. N. Current Organic Chemistry 2003, 7,

105, (13), 3311.

65.

Medforth, C. J.; Senge, M. O.; Smith, K. M.; Sparks, L. D.; Shelnutt, J. A. J. Am.

Chem. Soc. 1992, 114, (25), 9859.

66.

Haddad, R. E.; Gazeau, S.; Pecaut, J.; Marchon, J.-C.; Medforth, C. J.; Shelnutt, J. A.

J. Am. Chem. Soc. 2003, 125, (5), 1253.

67.

Ryeng, H.; Ghosh, A. J. Am. Chem. Soc. 2002, 124, (27), 8099.

29 68. Nguyen, K. A.; Day, P. N.; Pachter, R.; Tretiak, S.; Chernyak, V.; Mukamel, S. J.

Phys. Chem. A. 2002, 106, (43), 10285.

69. 70. 71.

Senge, M. O.; Kalisch, W. W. Inorg. Chem. 1997, 36, (26), 6103. Nguyen, K. A.; Day, P. N.; Pachter, R. J. Phys. Chem. A 1999, 103, 9378. Baerends, E. J.; Ricciardi, G.; Rosa, A.; van Gisbergen, S. J. A. Cood. Chem. Rev.

2002, 230, 5.

72.

Cheng, B.; Munro, O. Q.; Marques, H. M.; Scheidt, W. R. J. Am. Chem. Soc. 1997,

119, (44), 10732.

73.

Zhang, Y. H.; Ruan, W. J.; Li, Z. Y.; Wu, Y.; Zheng, J. Y. Chemical Physics 2005,

315, 201.

74. 75. 76.

Hohenberg, P.; Kohn, W. Phys. Rev 1964, 136, B864. Kohn, W.; Sham, L. J. Phys. Rev. A 1965, 140, 1133. Klapotke, T. M.; Schulz, A., Quantum Chemical methods in main group chemsirty.

John Wiley & Sons, Inc.: New York, 1998. 77. 78. Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 58, 1200. Young, D. C., Computational chemistry: a practical guide for applying techniques to

real world problems. Wiley- Interscience: New York, 2001.

79. 80. 81. 82.

Becke, A. D. Phys. Rev. A 1998, 38, 3098. Perdew, J. P. Phys. Rev 1986, B33, 8822. Runge, E.; Gross, E. K. U. Phys. Rev. Lett. 1984, 52, 997. Rosa, A.; Ricciardi, G.; Gritsenko, O.; Barends, E. J. Structure. Bond. 2004, 112, 49.

30 CHAPTER 2: MATERIALS AND METHODS Materials All the solvents used were HPLC grade and used without further purification. (Toluene (99.5+%, Aldrich, Spectrophotometric grade), benzonitrile (99.9%, Sigma, HPLC grade), pyridine(99.9%, Sigma, HPLC grade), DMF (99.9%, Sigma, HPLC grade)). All metallotetraphenyltetrabenzoporphyrins(MTPTBP), M= Cr, Mn, Co, Ni, Cu and Zn were bought from Frontier Scientific, Inc. and used as received. Instrumentation and Methods UV-visible Absorption Spectrometry The ground state electronic absorption UV-visible spectra were recorded using a Varian Cary 50 Bio (Varian Corporation) single beam spectrophotometer. All spectra were recorded at room temperature (295 K) using 2 mm or 1 cm path length quartz cuvettes.

Steady state Fluorescence Spectrometry Steady state fluorescence spectra were measured at room temperature using a PTI Instruments spectrofluorimeter (QM-4/2006-SE) equipped with a 75 W Xe lamp as excitation source and a R-928 PMT detector for the UV-Vis region. Near-IR signals were monitored at the right angle geometry using a Peltier cooled InGaAs detector with lock-in amplification. Luminescence spectra were acquired at room temperature and all solutions in 10 mm x 10 mm path length quartz cuvettes were Ar-saturated prior to luminescence experiments. Appropriate filters were used to avoid scattered light entering the detection system. All spectra were corrected for the sensitivity of the detector. All the photophysical experiments were performed using optically dilute solutions (OD = 0.080.1). For near IR emission the concentrations of the samples were ~ 6 m, providing optical absorption in the Q band maximum of ~ 1.2.

31 The fluorescence quantum yields (F) were measured using Zn mesotetraphenylporphyrin (ZnTPP) as a standard with a known quantum yield of 0.33 in deaerated benzene. The reference and the samples were excited at the same wavelength, where they had the same absorbance. (A = 0.05 a.u.) The areas under the fluorescence spectra (G) were measured and fluorescence quantum yields were calculated using the following equation.

sample =

Gsample Asample

GZnTPP ( ref ) AZnTPP ( ref )

2 sam.solution X 2 X ZnTPP ( ref ) ref .solution

G= Area/Intensity A=Absorbance of the sample at excited wavelength ref= Quantum yield of the standard

= viscosity of the solvent; benzene=1.50112; pyridine = 1.51016; toluene = 1.4969

Transient Absorption Experiments The early time events that follow photoexcitation of studied compounds were examined by femtosecond transient absorption spectrometry with 100 fs excitation pulses and the transient absorption signal at times longer than 10ns was monitored using nanosecond flash photolysis on Ar saturated solutions using excitation pulses of 8 ns duration.

Femtosecond Transient Absorption Spectroscopy The set up for the femtosecond pump-probe experiments at the Ohio Laboratory for Kinetic Spectrometry is represented in Figure 2.1. A Spectra-Physics Hurricane laser system was used as the excitation source. This includes a Ti:sapphire seed laser (Mai Tai, cw diode pumped, mode-locked pulsed laser), a pump Nd:YLF laser (Evolution, diode-pumped Q switched), a pulse stretcher, a Ti:sapphire regenerative amplifier and a pulse compressor. The

32 seed laser generated femtosecond pulses as short as 60 fs at an 80 MHz repetition rate with average power 700 Mw. The pulses are stretched using diffraction gratings and then amplified in a Ti-sapphire regenerative amplifier pumped by an Evolution Q-switched Nd:YLF laser. The fundamental output of the laser system consists of pulses of 800 nm, 1 mJ/pulse, 100 fs (FWHM) operating at a repetition rate of 1 kHz. This output was first split into two parts to generate pump (95%) and probe (5%). The pump beam generates the excitation pulse and the 5% generates a white light continuum that probes the absorption of the excited molecules generated by the pump pulse. The pump beam is converted to selected excitation wavelengths by coupling it into a second harmonic generator (CSX) for 400 nm excitation or into an optical parametric amplifier (Spectra-Physics OPA 800C) for wavelengths in the 320-700 nm. The pump beam is passed through an optical chopper (DigiRad c-980) rotating at a frequency of 100 Hz in order to switch the sample between excited and ground states. The probe beam is sent through a computer controlled delay line (Newport Corp. MTL250 PP 1250 mm linear positioning stage). The delay line provides an experimental time window of about 1.6 ns with a step resolution of 6.6 fs. Subsequently the 800 nm probe is focused onto a 3 mm thick sapphire plate (Crystal Systems, Inc., HEMLUX grade) that generates a white light continuum (450-750 nm). Prior to white light generation, the beam was passed through an iris diaphragm, a polarizer and a half wave plate in order to adjust the beam intensity delivered to the continuum generator. A spherical (f = 10 cm) mirror focuses the beam to the back of the sapphire plate to avoid additional chirp1 and another spherical mirror (f = 5 cm) after the sapphire plate collimates the white light beam prior to the sample cell. The mirrors were used to minimize the chirp of the white light continuum. A horizontal XY translation stage was employed to optimize the position of the sapphire plate.

33 The white light continuum probe beam was directed into the sample cell, superimposed on the pump beam at an angle of approximately 5o. The energy of the probe pulses was < 5 J at the sample. After passing through the sample cell, the probe continuum was coupled into a 400 m optical fiber and then connected to a CCD spectrograph (Ocean Optics, PC 2000) for time resolved spectral information. (450-850 nm) The CCD spectrograph was externally trigged by the chopper in order to distinguish between the continuum spectra corresponding to the ground and excited states of the sample. The delay line and the CCD spectrograph were computer-controlled by LabVIEW(National Instruments) software developed by Ultrafast Systems LLC (www.ultrafastsystems.com) allowing an automatic spectral acquisition over a series of delay times. The samples were continuously flowed during the experiments using a 2 mm flow cell (Quartz, Starna Cells) and the absorption spectra of the solutions were measured before and after the experiments to ascertain that minimal sample decomposition had occurred during the experiment. The instrument rise time was ca.150 fs (measured by an anti-Stokes Raman scattered peak width in toluene). At each time delay setting, dispersed absorption spectra were recorded for 2 seconds and the set averaged. Data points were recorded every 50 fs for the first 55 ps, or so and less frequently for longer delay times.

34
Chopper M M M M M

FM

OPA 800 CF

Continuum generator PM PM

1
Stretcher

FM Delay stage Sample

BS

Mai Tai diodepumped mode-locked Ti: sapphire laser

CCD spectrograph

Figure 2.1. The schematic representation of the ultrafast transient absorption setup. MMirror; FM-Flipping mirror; PM-Parabolic mirror; BS-Beam splitter

Nanosecond transient Absorption Figure 2.2 shows a schematic of the nanosecond laser flash photolysis system. The set up included a Q-switched Nd:YAG laser (Spectra Physics Quanta Ray GCR-230) and a computer aided kinetic spectrometer. The laser can be switched to obtain the frequency doubled output at 532 nm and frequency tripled output at 355 nm (6 ns, 10 Hz) and the energy was kept between 0.5 and 3 mJ per pulse. The kinetic spectrophotometer is described in details elsewhere2-4 and a brief description with recent modifications are as follows. The transient absorption was monitored at right angle using white light (probe) from a 150 W xenon CW arc lamp (Oriel Corporation). The probe beam was focused through the sample and re-imaged on the entrance slit of a Spex 1681 (0.22 m) monochromator. The

Regenerative amplifier

Q switched frequency diode Nd:YLF evolution laser

CSK super tripler

35 monochromatic light was detected with a modified Hamamatsu R928 PMT (5 instead of typical 9 stage dynode amplification) operating with a Keithley 247 high voltage supply. The resulting signal was routed through a DC-coupled back-off circuit that stored and displayed digital readouts for the intensity of the monitoring beam. A fast shutter (Uniblitz VMM-D1) was used to minimize the exposure of the sample to the probe light. The real time signal from the PMT was sent through a back-off circuit to eliminate a DC offset from the PMT and then was sent to a digital oscilloscope which averaged the signal over a pre-determined number of shots (typically 16-32). The counter/timer board (National Instruments NI-TIO) synchronized the Nd:YAG laser, fast shutter driver and oscilloscope and data were collected using in-house software routine written in LabVIEW (National Instruments), which generated the absorption difference spectra. The kinetic profiles were obtained in the same manner collecting data at one particular wavelength and averaging over 16-32 shots. Appropriate filters were used to avoid scattered light from laser beam entering the PMT. To obtain transient absorption spectra, solutions were Ar saturated prior to the experiment. Kinetic profiles were recorded in Ar, air and O2 saturated solution which enabled the measurements of oxygen quenching rate constant when necessary. The data analyses were done using standard data analysis software using Origin (Origin Lab Corporation).

36

Nd:YAG laser Third harmonic generator

PMT

Monochromator Sample back- off

Shutter Xe lamp

oscilloscope

Figure 2.2. Schematic diagram of the nanosecond laser flash photolysis system

Computational Details For all calculations the Amsterdam Density Functional ADF suite of Programs (release 2004.01 or 2005.01.11,12, SCM, Amsterdam) have been used. The calculations exploited the local density approximation (LDA) functional of Vosko-Wilk-Nusair (VWN)5 together with the generalized gradient approximation (GGA), employing Becke's6 gradient approximation for exchange and Perdew's7 for correlation (BP). Corrections for relativistic effects were employed in calculation for Pd and Pt complexes by using the Zeroth Order Regular Approximation (ZORA) scalar Hamiltonian.8, 9 The excitation energies and oscillator

37 strengths were calculated using time-dependent density functional theory (TDDFT) as implemented in the ADF code.10, 11 In brief, the solution of the TDDFT response equations is obtained as a result of iterations starting from the usual ground state or zeroth-order Kohn Sham (KS) equations.11 approximate to the usual static exchange-correlation (xc) potential xc (r). After the solution to the ordinary KS equations has been obtained, the first order density change has been calculated from an iterative solution to the first order KS equations. There, an approximation to the first functional derivative of the time-dependent xc potential xc (r,t) with respect to the time-dependent density (r, t), the so-called xc kernel was used.12 For the xc kernel, the Adiabatic Local Density Approximation (ALDA) was employed. When this approximation is used the time dependence (or frequency dependence referring to the Fourier-transformed kernel) should be neglected, so that the differentiated static LDA expression can be used. In this work the Vosko-Wilk-Nusair parameterization was utilized.5 For the exchange correlation potentials which appear in the zeroth-order KS equations, the same GGA as in the DFT calculations was employed. For calculations the standard all electron ADF TZ2P basis set, which is an uncontracted triple- STO basis set with one 3d and one 4f polarization function for C, N and O atoms, one 2p and one 3d polarization function for H, a triple- 3d, 4s basis with one 4p and one 4f function for Co, Ni, Cu and Zn, a triple- 4d, 5s basis with one 5p and one 4f function for Pd, and a triple- 4f, 5d, 6s basis with one 6p and one 5f function for Pt was used. For the Pd and Pt complexes the core densities were computed relativistically by the Dirac auxiliary program. Geometry optimizations were performed for the ground and selected triplet excited states of the studied compounds. Open-shell DFT calculations for the triplet states were performed within a spin-unrestricted formalism. The optimized ground state and excited state structures were verified to be true minima by frequency calculations. All

38 calculations were performed in the gas phase. The molecular orbitals were visualized with the Graphical User Interface for the ADF package (ADF GUI).

Estimation of the MTPTBP triplet (,*) energies from the oxygen quenching bimolecular rate constant The energies of the triplet state of porphyrins were calculated using bimolecular rate constant of the quenching of the T1 by molecular oxygen. Following scheme has been used to represent the energy transfer process from the triplet state localized on the system to the ground state oxygen.13-15 kq
3

(M()TPTBP kT
1

)+

O2 ( g) kb

(M()TPTBP )+ O2 ( 1g ) k O2 (3 g)

(M()TPTBP)

- kq = the rate constant for the energy transfer from the triplet state porphyrins to ground state molecular oxygen ( from Table 6.4); - kT, k = the intrinsic rates of decay of macrocycles T1 and O2( 1g ) - kb = rate constant for the back reaction. The back reaction can be considered as diffusion limited reaction. It depends on the solvent viscosity and the temperature and can be calculated from the Debye equation: K diff =

8kBT = 1.1 x 1010 M-1S-1 3

For toluene = 0.589 Cp at 298 K from ref.16 -equilibrium constant for the T1 quenching reaction, Keq = kq/kdiff, where kb=kdiff) From Keq, triplet energy ET can be obtained, according to; ET E + RT ln(1/9) = RT ln Keq

39 Where; E = 22.54 kcal/mol for the O2 ( 1g ) O2 (3 g) (0,0) transition in oxygen RT ln(1/9) = 1.3 kcal/mol ; ln 1/9 is the spin-statistical factor and it accounts that only one-ninth of the intervening collision complexes are of overall singlet multiplicity17 The calculated data are collected in Table 6.5.

References 1. 2. 3. Cerullo, G.; De Silvestri, S. Rev. Sci. Instrum. 2003, 74, 1. Nikolaitchik, A. V.; Korth, O.; Rodgers, M. A. J. J. Phys. Chem. A 1999, 103. Pelliccioli, A. P.; Henbest, K.; Kwag, G.; Carvagno, T. R.; Kenney, M. E.; Rodgers,

M. A. J. J. Phys. Chem. A 2001, 105, 1757. 4. Rihter, B. D.; Kenney, M. E.; Ford, W. E.; Rodgers, M. A. J. J. Am. Chem. Soc. 1990,

112, 8064. 5. 6. 7. 8. 9. 10. Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 58, 1200. Becke, A. D. Phys. Rev. A 1998, 38, 3098. Perdew, J. P. Phys. Rev. A 1986, B33, 8822. van Lenthe, E.; Barends, E. J.; Snijders, J. G. J. Chem. Phys 1993, 99, 4597. van Lenthe, E.; van Leeuwen, R.; Barends, E. J. Quantum Chem 1996, 57, 281. van Gisbergen, S. J. A.; Snijders, J. G.; Baerends, E. J. Comput. Phys. Commun. 1999,

118, 119. 11. 9347. 12. Rosa, A.; Ricciardi, G.; Baerends, E. J.; van Gisbergen, S. J. A. J. Phys. Chem. A van Gisbergen, S. J. A.; Snijders, J. G.; Baerends, E. J. J. Chem. Phys. 1995, 103,

2001, 105, 3311. 13. Firey, P. A.; Ford, W. E.; Sounik, J. R.; Kenney, M. E.; Rodgers, M. A. J. J. Am.

Chem. Soc. 1988, 110, (23), 7626.

40 14. Gunaratne, T.; Kennedy, V. O.; Kenney, M. E.; Rodgers, M. A. J. J. Phys. Chem. A

2004, 108, 2576. 15. Rihter, B. D.; Kenney, M. E.; Ford, W. E.; Rodgers, M. A. J. J. Am. Chem. Soc. 1993,

115, 8146. 16. Montalti, M.; Credi, A.; Prodi, L.; Gandolfi, M. T., Handbook of Photochemistry.

Taylor & Francis Group, LLC: New York, 2006. 17. Soldatova, A. Ph.D Thesis, Bowling Green State University, Bowling Green, 2007.

41 CHAPTER 3: THE PHOTOPHYSICAL PROPERTIES OF ZINC AND NICKEL TETRAPHENYLTETRABENZOPORPHYRINS: A COMBINED EXPERIMENTAL AND THEORETICAL INVESTIGATION Abstract The ground and excited state properties of Zn()TPTBP have been investigated by a combination of DFT/TDDFT and transient absorption spectrometry in order to provide experimental and theoretical evidence on the spectral properties of the -localized singlet and triplet states of the tetraphenyltetrabenzoporhyrin macrocycle. The results were compared with Ni()TPTBP. Specifically Zn() and Ni(), were chosen to study the effect of filled and half- filled d orbitals on the photophysical properties on porphyrin macrocycle. In Zn()TPTBP, 640 nm excitation produced a vibrationally hot -localized S1 state. After cooling, it decayed to the 3,* excited state where ground state repopulated with ca.236 s lifetime in pyridine. The lifetime of the singlet state 1,* was found to be ca.235 ps in benzonitrile and ca.340 ps in pyridine. Fluorescence from the S1 state was observed with quantum yield of 0.008. Transient absorption spectrometry with femtosecond time resolution was employed along with DFT/TDDFT calculations to provide a detailed understanding of the sequence of events that follow Q band photo-excitation.

Introduction Zn porphyrins are generally employed as reference complexes for other metallotetrapyrroles. And also these type of complexes have been investigated for potential components in various molecular electronic devices.1-7 For example, Zn porphyrins have been utilized as photosensitizers in self-assembled supramolecular dyads1 or triads2, 8 together

42 with fullerene. Water-soluble zinc porphyrins have been used to photosensitize water reduction and oxidation.9, 10 The metal ion to which the tetrapyrrole macrocycle is ligated plays a vital role in the excited state deactivation. Having a d10 electronic configuration, Zn has completely filled dorbitals and belongs to a class of regular porphyrins according to Goutermans classification.11 The optical absorption and emission spectra of regular porphyrins are determined by the electrons of the ring, with only minor perturbation from the electrons of the central metal. As a result, the interactions between the porphyrin -system and the metal are small and the photophysical properties are mainly governed by the macrocycles system. Zn() has been selected for study as the prototype to investigate the photophysical properties that are mainly controlled by the system. When the central metal is a transition metal having vacant or partially filled d-orbitals, such as Ni, Co, Fe, Pd, etc., the excited state deactivation can be governed by the electronic states that are formed by the interactions between orbital and the metal d-orbital manifold that can be situated at lower energy than the pure * states. Such low-lying states can be intermediate in the cascade of deactivation process by providing the series of low energy radiationless transitions.12 The deactivation of the Zn porphyrin S1 state occurs predominantly through the formation of the -localized triplet state and through the fluorescence to the ground state. The lifetime of the S1(,*) of Zn() compounds has been found to be ~ 2.5 ns.13 Examination of the Zn porphyrins literature reveals information about the above mechanism and some examples (in fluid solutions at room temperature) are as follows; The quantum yield of triplet state for Zn()TPP was found to be 0.82 while the fluorescence quantum yield was 0.04. The triplet state lifetime in the absence of oxygen was 1.2 ms and the fluorescence lifetime was 2.7 ns.14 For Zn()TMPy, the quantum yield of triplet state was

43 found to be 0.90 and the fluorescence quantum yield was 0.02. The triplet lifetime was 1.30 ms in deaerated solution and the fluorescence lifetime was 1.3 ns.14 For Zn()OEP, the fluorescence quantum yield was 0.04 and the fluorescence lifetime was 2.2 ns.15 Photophysics of the higher electronic states (S2) of zinc porphyrin have also been studied and it was reported that the S2 state deactivates with the life time 1-2 ps via internal conversion into the S1 state.16-18 Ni() has a d8 electronic configuration. When there are no axial ligands attached (in non-coordinating solvents), Ni porphyrins are low spin with dz2 being the highest occupied d orbital and dx2-y2 is the lowest unoccupied d orbital. One-electron excitation, related to the transition of an electron from dz2 orbital to the higher dx2-y2 orbital, gives rise to singlet and triplet d,d states. When the central metal ion has unfilled d orbitals, these can couple with the -system and provide additional deactivation pathways. Extended Hckel calculations and the lack of luminescence suggested that the normally emissive (,*) excited state of the porphyrin macrocycle becomes deactivated to produce the lower lying singlet or/and triplet metal-centered (dz2, dx2-y2) excited state.11, 19 The mechanism of deactivation of the excited states of planar porphyrins proceeds via a sequence of electronic deactivation steps, (,*)(d,d)ground state.20, 21 For example, the (,*) excited states of Ni(II)TPP and Ni(II)OEP have been shown to form (d,d) states within 1 ps13, 22, 23; these d,d states repopulate their ground states in 200-500 ps. 24-28 Apart from the coupled conformational and electronic changes that take place subsequent to excitation of Ni porphyrins, the other interesting feature is that the excited metal-centered state is generated vibrationally hot. Holten et al observed that excited d,d states in non-coordinating solvents displayed a blue-shift and wavelength dependent kinetics on the 5-25 ps time scale as vibrational cooling occurred.13, 22, 23

44 In this chapter, the photophysical properties of Zn()TPTBP are investigated by means of transient absorption spectrometry and using theoretical characterization of the molecule and electronic structure of the ground state and the excited state. A comparison with Ni()TPTBP12 (already published) is made in order to have insight of the effect of the central atom on the deactivation pathway.

Theoretical characterization of Zn()TPTBP Ground State Molecular Structure Analysis The DFT optimized molecular structure of the Zn()TPTBP complex is presented in Figure 3.1.

Figure 3.1. Top view of the DFT-optimized molecular structure of Zn()TPTBP with atom labeling.

The calculations reveal that the complex adopts a D2d saddled confirmation with the phenyl groups twisted out of the porphyrin plane by 70o (the porphyrin-phenyl dihedral angle-

45 < (C2C1Cmeso)) was similar to the other compounds studied. The dihedral angle between the adjacent pyrrolic nitrogens that characterizes saddling of the macrocycle plane is < (C NNC)ad 25o. Ni()TPTBP also has adopted a D2d structure with a saddled conformation.12 The optimized geometrical parameters for both complexes are listed in Table 3.1. Similar to tetraphenytetrabenzoporphyrins, the Zn and Ni octabutoxy phthalocyanines and naphthalocyanines (ZnNc(OBu)8/ ZnPc(OBu)8 and Ni Nc(OBu)8/ NiPc (OBu)8) have been shown to have D2d symmetry in order to minimize the steric repulsion between the lone pair of facing oxygen atoms belonging to the methoxy groups.29, 30 The tilting of phenyl groups is necessary to relieve the steric hindrance making possible for phenyl rings to rotate toward the mean porphyrin plane.31, 32 Parameter MN C N C C C C C Cm Cm Co Co Co C Cmeso Cmeso C1 C1 C2 C2 C3 C3 C4 CNC NCC CCmesoC C2C1CmesoC (CNNC)op (CNNC)ad Ni()TPTBP 1.922 1.384 1.454 1.413 1.405 1.395 1.406 1.395 1.494 1.403 1.402 1.399 107.4o 109.4o 121.4o 70o 0o 25.2o Zn()TPTBP 2.048 1.377 1.461 1.418 1.405 1.390 1.404 1.409 1.496 1.402 1.396 1.397 109.2o 108.7o 125.3o 70o 0o 21.5o

Table 3.1. Selected Bond Distances (Ao) and Bond Angles (deg) calculated for M()TPTBP in the D2d confirmation.

46 The central metal-pyrrolic nitrogen distance for Zn()TPTBP (2.048 Ao) is larger than that found for the first row transition metal complexes with partially filled d shells. This is a result of the repulsion between the filled 3dx2-y2 metal orbital and the lone pairs of the pyrrolic nitrogens.

Ground State Electronic Structure Analysis The ground state energies of the highest occupied and the lowest unoccupied molecular orbitals calculated for both Ni and Zn complexes in the D2d confirmation are shown in the Figure 3.2. The atomic orbital population analysis for the orbitals represented in Figure 3.2, calculated for Zn complex is given in Appendix A. For the Ni complex the data are taken from ref.12.

-1.5 -2.0 -2.5 -3.0 -3.5 E/eV -4.0 -4.5 -5.0 -5.5 -6.0 -6.5 NiTPTBP
16a2 18b1 40e

17a2

40e

dx -y
2

23b2

18b1 22b2

dz 23a 1
2

22b2

d 39e
38e 22a1 23a1

39e 23b 2 16a2 38e

ZnTPTBP

Figure 3.2. Energy level scheme for Zn()TPTBP and Ni()TPTBP. Goutermans HOMO, HOMO-1 and LUMO orbitals are depicted in red.

47 Metal d orbitals lying in close proximity to Gouterman HOMO and LUMO are likely to be responsible for fast non-radiative decay and it is worth paying attention to those orbitals in the Ni()TPTBP. The 23b2 dx2-y2, virtual orbital lies between the HOMO and LUMO. The Zn 3d orbitals lie too low in energy to play any role in the deactivation of the S1 state. Contour plots of the Zn()TPTBP, together with the energy levels are given in Figure 3.3.

-1
17a2

-2
17a2

40e

40e:yz

40e:xz

-3 E/eV -4 -5

18b1

22b2 23b2

18b1 22b2 39e

39e:yz

39e:xz

-6

23a1 16a2

16a2

23b2 23a1

38e:yz

38e:xz

38e

Figure 3.3. Contour plots of the Zn()TPTBP, together with the energy levels.

The four orbitals that are responsible for the appearance of the main spectroscopic bands on the ground state absorption spectrum, according to Goutermans four orbital model33 are HOMO 18b1, HOMO-1 22b2 and an unoccupied set of degenerate 40e orbitals. The HOMO 18b1 has contributions mainly from the C, Cm and Co, while the electronic density on the HOMO-1 is largely localized on the pyrrolic nitrogen and meso- carbon atoms. (Appendix A) The G-LUMO, which is an unoccupied set of degenerate 40e orbitals are

48 primarily located on the C and C atoms. In Zn it is composed of a small contribution from pyrrolic nitrogen (12%) while with Ni it has a small contribution from the metal 3d orbital. (4%) Excited States and Ground State Absorption Spectra Figure 3.4 shows the room-temperature ground state absorption spectra of zinc and nickel tetrabenzoporphyrins in toluene solution normalized to unit absorbance at the B band maximum.

1.0 normalized absorbance 0.8 0.6

448nm 462nm NiTPTBP ZnTPTBP

645nm 0.4 652nm 0.2 0.0 300

400

500

600

700

wavelength/nm

Figure 3.4. Ground state absorption spectra of M()TPTBP complexes in toluene, M=Zn, Ni The Q band corresponds to the transition to the macrocycles lowest 1(,*) excited state with a weak vibrational progression to the blue; the intense B band corresponds to the transition to the second excited singlet state. The position of the B and Q bands were shifted to higher energy when going from Ni to Zn complexes. Red shifts of the Q band have been observed with metallo-octabutoxynaphthalocyanines along the Co, Ni, Cu series.34-36 TDDFT calculations were performed for the lowest optically allowed excited states of Zn complex and their excitation energies and oscillator strengths related to the appearance of the Q band are presented and compared to the experimental data for the Ni complex in Table 3.2. For both compounds 11E state is responsible for the appearance of the Q band. This state

49 has substantial oscillator strength (on the contrary to common porphyrins) and is mainly derived from the one electron transition from the G-HOMO 18b1 to the set of unoccupied 40e orbitals. Due to considerable separation in energy between the Gouterman HOMO and HOMO-1, the contribution from the 22b2 40e one electron transition to this state is minor. For Zn, the energy gap between HOMO and HOMO-1 is 0.37 eV and has 27% contribution. Ni has a higher energy gap between HOMO and HOMO-1 (0.55 eV) resulting in even less contribution to the composition of the Q band (16%). For the Zn complex, the Q band is computed at 1.89 eV and experimentally it can be seen at 1.90 eV. The theoretical results are consistent with the observed red shifs of the B and Q band when going from Ni to Zn. TDDFT state
1 Zn()TPTBP 1 E(Q)

Exp. f 0.131 E(eV/nm)a 1.90(652)

Composition(%) Eva(eV/nm) 18b1 40e(71) 22b2 40e(27) 1.89(656)

21E(B)

22b2 40e(59) 18b1 40e(21) 23b2 40e(11)

2.62(473)

1.52

2.68(462)

1 Ni()TPTBP 1 E(Q)

18b1 40e(82) 22b2 40e(16)

1.94(640)

0.21

1.93(643)

51E(B)

22b2 40e(58) 38e 23b2(21) 18b1 40e(10)

2.72(456)

0.95

2.78(447)

Table 3.2. Vertical excitation energies (Eva) and oscillator strengths (f) computed for the lowest optically allowed excited states of Zn() and Ni()TPTBP.a data taken in toluene at room temperature.

50 The near-degeneracy of the G-HOMO and G-HOMO-1 that exists in porphyrins,37, 38 does not occur in the benzoporphyrin derivatives due to the electronic effect of benzoannulation and it partially removes mixing of the Gouterman one-electron transitions. This makes cancellation of the transition dipole moments in the Q band less effective, resulting in the enhanced oscillator strength of the Q band. In the Zn complex, the large oscillator strength, of 1.52 at 2.62 eV (473 nm) accounts for the intense B band at 462 nm in the ground state absorption spectrum. This state arises from the mixing of the Gouterman one-electron transitions 22b2 40e (59%), 18b1 40e (21%) and 23b2 40e (11%). In the Ni complex, the 51E is responsible for the B band with similar transitions as Zn. In addition, the Ni complex has a small contribution from an LMCT transition. There are no states between the Q band and B band related with Zn complex while an abundance of states can be found with Ni complex.

Optically Silent Excited States Below the S1(*) State Since the excited state deactivation pathway in the Zn complex is mainly governed by the triplet (,*) state, the triplet excited states below the Q state were also been examined. Table 3.3 lists their vertical absorption energies, Eva, related to the Franck-Condon transitions from the ground state, together with adiabatic, Eadia and vertical emission Eve energies. The relative energies and characters are important to understand the fast non-radiative decay of the optically produced excited states, especially with Ni case. In addition to 3(,*) T1 state, there are six states below the Q state can be found in Ni()TPTBP. The details of the states were gathered in reference 12. The lowest triplet state in Zn()TPTBP is the 13E(*) state, which can be found 1.52 eV vertically above the S0 state.

51 TDDFT state Composition(%) character Zn()TPTBP 23E 13E 23b2 40e(99) 18b1 40e(99) * * Eva 1.86 1.52

Table 3.3. Excitation energies (eV) obtained for the low-lying excited states of Zn()TPTBP Many metalloporphyrins undergo pseudo Jahn-Teller distortions because of the neardegeneracy of the a1u and a2u orbitals in the HOMO.39 The Jahn-Teller postulate says any non-linear molecular system in a degenerate electronic state will undergo distortion to form a system of lower energy removing the degeneracy.40 Normally Zn porphyrins are expected to undergo Jahn-Teller distortions into a D2 or C2v structure along the b1 or b2 active modes.30, 41,
42

Therefore to examine the effect of vibrational relaxation shift of the 13E(*) S0

transition, geometry optimization was performed for the 13E, the lowest triplet state. It was found that the C2v was the most stable structure. In the Ni complex, the 21E has mixed d,dx2-y2/MLCT and its triplet 23E is doubly degenerate and has undergone a Jahn-Teller distortion into a C2v structure.12 Unlike the Zn complex, the 1B2/3B2 splitting was found to be larger than 1E/3E splitting because of the more prominent d,d character associated with one electron transitions.43

Steady-State Fluorescence and Transient Absorption Experiments Steady-State Fluorescence Measurements Steady-state fluorescence and ground state absorption spectra in the Q band region for Zn()TPTBP in pyridine solution were normalized to unit amplitude at their respective maxima and displayed in Figure 3.5.

52

normalized absorbance and fluorescence

1.0 0.8 0.6 0.4 0.2 0.0 550 absorption fluorescence

600

650 700 wavelength/nm

750

800

Figure 3.5. Normalized absorption (black) and steady state fluorescence (red) spectra of Zn()TPTBP in pyridine at room temperature. The fluorescence spectrum was obtained in argon saturated pyridine with 442 nm excitation.

The fluorescence spectrum of Zn()TPTBP has a mirror-symmetry relationship to the ground state absorption band in the Q band region showing that it undergoes minimal nuclear geometry change on excitation. The fluorescence originated from the first excited singlet state(Q(0,0)) with maxima at 668 nm and a weak fluorescence band(Q(0,1)) at ca. 1290 cm-1 to the red of the Q(0,0) maxima. The fluorescence quantum yield for the Zn()TPTBP was estimated according to equation 1 in chapter 2 using Zn meso-tetraphenylporphyrin (ZnTPP) as a standard with a known quantum yield of 0.33 in deaerated benzene.34 The radiative lifetime was calculated from the Strickler-Berg equation,44 as described in chapter 2. The Stokes shift between the fluorescence and absorption maxima is 250 cm-1. When transitions are allowed and little changes in the geometry of the excited state are observed, the Strickler-Berg equation has proved to calculate the radiative lifetimes with good precision. For Zn complex, the ( *) transition responsible for the Q band is highly allowed making it more appropriate in calculating the radiative lifetimes.45 Fluorescence quantum yield (F) of Zn()TPTBP was

53 found to be 0.008 and the calculated radiative lifetime was found to be ~ 2 ns, in good agreement with the published 1.5 ns lifetime, measured in benzene.34 Phosphorescence of Zn()TPTBP at room temperature in deoxygenated pyridine was not observed.

Transient Absorption Experiments Femtosecond Transient Absorption The Zn complex was investigated in order to provide experimental evidence for the spectral properties of the -localized singlet and triplet states of the tetraphenyltetrabenzoporhyrin macrocycle keeping in mind that the metal orbitals do not contribute to the ,* basic electronic condition. Since Zn()TPTBP was unstable in toluene, transient absorption spectra were carried out in pyridine solution. Figure 3.6 shows the temporal evolution of the transient absorption signal for Zn()TPTBP in pyridine upon excitation at 640 nm at different delay times.
0.10 2.69 ps 107.49 ps 394.71 ps 1107.05 ps

0.05

0.00

-0.05 500 550 600 650 700 750 800

wavelength/nm

Figure 3.6. Femtosecond transient absorption difference spectra of Zn()TPTBP in pyridine at different delay times in the wavelength region 500-800 after 640 nm excitation.

Figure 3.7 shows the temporal evolution of the transient absorption signal for Zn()TPTBP in benzonitrile at 2 ps and 1000 ps upon excitation at 640 nm.

54
1.0

normalized A

0.5

0.0 2.29 ps 1075.1 ps

-0.5

-1.0 500 550 600 650 700 750 800

wavelength/nm

Figure 3.7. Femtosecond transient absorption difference spectra of Zn()TPTBP in benzonitrile at 2 ps and 1000 ps, normalized to the positive absorption maxima in the wavelength region 500-800 nm after 640 nm excitation.

The spectrum formed within the instrument response time (200 fs) showed a broad positive absorption interrupt by the bleaching signal due to the Q band region of Zn()TPTBP centered near 660 nm. A strong transient absorption at 500 nm was observed. As the time evolved the positive absorption maxima shifted slightly to the red with the maximum at ca.530 nm having a different shape indicating the formation of a new transient species. As with the other complexes, ultrafast experiments on Zn()TPTBP were also done in benzonitrile solution. The spectra related to 2 ps and 1000 ps normalized to the positive absorption maxima in the wavelength region 500-800 nm after 640 nm excitation are depicted in Figure 3.7. Scrutiny of the figure reveals that the differences in spectral shape remained the same as in pyridine. Photoexcitation at 640 nm directly generates the Q state (see the ground state optical absorption spectrum in Figure 3.4) and the first observed transient will undoubtedly be the absorption spectrum of the Q state. The ca.3 ps spectrum of the Zn complex is thus assigned

55 to the S1 Sn transition of the system. As time passes, the S1 state undergoes intersystem crossing to the T1 state, as represented by the 1000 ps spectrum in Figure 3.6, peaking at 550 nm. Figure 3.8 shows the temporal profiles of the transient absorption displayed by Zn()TPTBP in pyridine solution following 640 nm excitation taken at four spectral regions.

0.10 0.08 0.06

A_507nm

0.025 0.020 0.015

A_610nm
1 = 1.88 0.29 ps (13%) 2 = 406.37 5.52 ps (87%)

1 =

0.7 0.07 ps (10%)

2 = 338.39 1.68 ps (90%)

0.04 0.02 0.00 0

0.010 0.005 0.000

200

400

600

800

1000 1200 1400

200

400

600

800

1000 1200 1400

wavelength/nm

wavelength/nm

0.016 0.014 0.012 0.010

A_692nm

0.020

0.015
1 = 1.98 0.07 ps (47%) 2 = 344.53 4.57 ps (53%)

0.006 0.004 0.002 0.000 -0.002 0

A_710nm

0.008

0.010
1 =

1.58 0.08 ps (25%)

0.005

2 = 326.19 3.51 ps (75%)

0.000
200 400 600 800 1000 1200 1400

200

400

600

800

1000 1200 1400

wavelength/nm

wavelength/nm

Figure 3.8. Femtosecond kinetics profiles of the transient absorption signal at various probe wavelengths for Zn()TPTBP in pyridine, excited at 640 nm. The decay of the positive absorption signal as well as the recovery of the negative signal were fitted by a double exponential function providing two lifetimes. The kinetic data for probe wavelengths ranging from 490 to 720 nm were analyzed in details. It was found

56 that the lifetime of the fastest component and its relative contribution to the overall decay showed strong wavelength dependence. A plot of this first lifetime with different wavelengths in the region 580 to 720 nm are displayed in Figure 3.8 with the transient absorption spectral cuts taken at 2 ps and 8 ps time delays. As can be seen the second component having longer lifetime also showed similar wavelength dependence; but it can be assigned as ca.340 ps. During the 10 ps or so the spectral shape of the positive absorption stretching from 500 nm to 640 nm does not change even though slight red shift can be observed where the bleaching occurs. (Figure 3.8 lower panel) The studies of solvent-induced vibrational relaxation processes of the S1 states with porphyrins have showed that the vibrational relaxation the rates are observed on the time scale of picoseconds to tens of picoseconds. 46-48 Given the consideration that exciting to the blue of the Q band generates vibrationally hot species, it is reasonable to assign the first exponential lifetime component to the cooling of the S1 state. The excess vibrational energy is first distributed among all the vibrational modes of the molecule and the cooling process occurs due to the solvent induced dissipation of excess vibrational energy within the S1 excited state. Figure 3.9 shows that the short lifetime lies close to the wavelength where the negative and positive absorptions cross. The wavelength dependent kinetics arise from the detailed nature of the upper and lower potential energy surfaces. When the origin state is hot, upward transitions originating closer to the classical turning points become increasingly probable.29 The vibrational states with high quantum numbers have a higher density of vibrational oscillators below them than states with lower quantum numbers. Therefore they will cool resulting in different wavelength regions having different cooling lifetime.

57

5 4 3

1/ps A

2 1 0

0.04 0.02 0.00 -0.02 -0.04 -0.06 600 625 650 675 700 725 wavelength/nm 1.46 ps 8.49 ps

Figure 3.9. Upper panel: first lifetime/wavelength dependence, Lower panel: two transient absorption spectral cuts taken at 2 ps and 8 ps time delays excited at 640 nm in pyridine solution.

The kinetic profiles in benzonitrile solution showed that it also follows the wavelength dependent kinetics as pyridine. And also it showed a bi-exponential decay kinetics having slower rise lifetime and the subsequent decay lifetime. Figure 3.9 shows the comparison of the kinetic profile at 520 nm of Zn()TPTBP in the solvents toluene and benzonitrile. It shows that in benzonitrile solution the lifetime for the S1 state is lower than that of pyridine.

58

1.0 0.8
A_520 nm
2 = ~ 344 ps

0.6 0.4 0.2 0.0 0 200 400 600 800 1000 1200 1400 wavelength/nm pyridine benzonitrile
2 = ~ 235 ps

Figure 3.10. Normalized kinetic profiles of the transient absorption signal at 520 nm for Zn()TPTBP in benzonitrile and pyridine solutions after 640 nm excitation.

The properties of solvents such as polarity and coordinating ability may alter the absorption as well as the decay characteristic of the excited states. For example the N atoms in pyridine and benzonitrile can bind to Zn center to form five and /or six coordinated species.49, 50 Additionally, the lone pairs on nitrogen or oxygen in the above solvents, give them the potential of coordinating to the central metal, stabilizing the chromophore by lowering the energy. The electron-donating ability increase in the order benzonitrile < pyridine.50 An exponential fit to the early part of the decay profile in Figure 3.7, generated a lifetime of 200-300 ps for the S1 state depending on the solvent corresponding to intersystem crossing to T1. The TDDFT calculations have confirmed that the (*) triplet is the only state below the S1. (Table 3.3) Wavelength dependent kinetics for vibrational relaxation has been described for various Ni porphyrins and phthalocyanines.13, 20, 22, 23, 43, 51 The experimental results of Ni()TPTBP demonstrated that the (,*) excited states deactivate through a metal-centered state. The excess vibrational energy was dissipated by

59 intra-molecular and intermolecular modes of vibrational relaxation and the cooled d,d state repopulated the initial ground state via a lower-lying charge transfer state.12

Nanosecond Transient Absorption Experiment To determine the lifetime of the localized triplet state, transient absorption measurements on the nanosecond scale were performed on deaerated solution of Zn()TPTBP in toluene solution and excited at 460 nm.(it was necessary to add 1% of pyridine by volume to the toluene solution in order to stabilize the complex.)

0.02 0.00 -0.02 -0.04 -0.06 -0.08 -0.10 400

470nm

542nm

657nm

3s 20s 50s 100s 200s 300s 400s 500s

500

600

700

wavelength/nm

Figure 3.11. Nanosecond transient absorption difference spectra of Zn()TPTBP in Ar saturated toluene (1% pyridine was added) solution at different delay times followed by 460 nm excitation. Vertical arrows indicate the evolution of the transient absorption signal.

Figure 3.11 shows the characteristic difference spectrum of the triplet state localized on the porphyrin macrocycle.34 The negative absorption bands in the B and Q band regions are due to the ground state bleaching. The maximum of the T1-Tn absorption band is around 542 nm, which corresponds to the maximum in the 1000 ps spectrum in figure 3.6.

60 There are clearly isosbestic points between the positive and negative absorption, indicating the simultaneous behavior of the transitions. Figure 3.12 LH panel, illustrates the decay profile of the transient absorption signal of the ZnTPTBP in pyridine/toluene solution at the absorption at 540 nm.
3000 2500
A_540nm_Ar

0.020

0.015

= 236.72 2.0s

2000
0.010

Ar/

1500 1000 500

3 -1

0.005

Ksv = (190.14 2.5)*10 M

0.000 0 100 200 300 400 500 600 700 800 time/s

0 0 2 4 6 8 concentration of O2 / mM 10

0.03
0.02 0.01
A_500nm_O2
A_500nm_air

0.02 0.01 0.00 -0.01 -0.02 -0.03 -0.04

1= 0.083 0.001 s

0.00 -0.01 -0.02 -0.03

= 0.40 0.004 s

-0.05
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 time/s

0.0

0.1

0.2

0.3

0.4 time/s

0.5

0.6

0.7

0.8

Figure 3.12. Left Upper: Nanosecond kinetic profile of the transient absorption signal in Ar saturated pyridine_toluene solution, exc = 460 nm. Solid red line is the fit to the experimental points and blue line represents the residuals of the fit. Right, Upper: determination of the rate constant for the quenching of the triplet 3(,*) state of Zn()TPTBP by oxygen. Left Lower: Nanosecond kinetic profile of the transient absorption signal in air saturated pyridine_toluene solution, exc = 460 nm Right Lower, Nanosecond kinetic profile of the transient absorption signal in air saturated pyridine_toluene solution, exc = 460 nm.

61 The triplet state lifetime was 237 s and it decayed directly to the S0 surface with isosbestic behavior at 442 nm, 492 nm, 627 nm and 680 nm. The decay of the triplet state was enhanced in the presence of oxygen, and the bimolecular oxygen quenching rate constant was obtained by measuring kobs in solution at different oxygen concentrations. The competition plot for the decay of the triplet state in the presence of oxygen is shown in the RH panel of Figure 3.12. The bimolecular rate constant was 1.2 x109 M-1s-1. The photophysical properties of Zn() TPTBP are summarized in Table 3.4. Photophysical Properties Q band/nm* 10-5Qband/ mM-1cm-1 fluor /nm F stokes/cm-1 S1/ps max T1 Tn/nm T1 in Ar/s 10-9 kq 652 47 668 0.008 250 380 560 236.7 1.2

Table 3.4. The photophysical properties of Zn()TPTBP. * Extinction coefficient in toluene with Q band maxima 652 nm. Triplet lifetimes were measured in 1% of pyridine_ toluene solution. All the other measurements were carried out in pyridine solution

Summary and Conclusions There are only two electronic states involved in the photo deactivation of Zn()TPTBP complex. The lowest excited state, which is identified as 11E is the photogenerated Q state and it has ,* character. The singlet state is generated in high vibrational levels and after vibrational cooling; the deactivation takes place mainly through the T1 triplet state in competition with a low quantum yield of fluorescence. The decay of the triplet state

62 occurs on the microsecond time scale. There are no metal-associated states such as low-lying metal centered (d,d) or charge-transfer excited states available as compared to Ni()TPTBP. S1

T1

700fs 340 ps

236 s S0

Reaction coordinate

Figure 3.13. Kinetic diagram for the excited state deactivation of Zn()TPTBP. Theoretical and experimental results gave enough evidence to explore about the influence of the central metal atom in the system on excited state deactivation.

References 1. D'Souza, F.; Deviprasad, G. R.; El-Khouly, M. E.; Fujitsuka, M.; Ito, O. J. Am. Chem.

Soc. 2001, 123, 5277. 2. D'Souza, F.; Deviprasad, G. R.; Zandler, M. E.; El-Khouly, M. E.; Fujitsuka, M.; Ito,

O. J. Phys. Chem. B 2002, 106, 4952. 3. 4. 5. Flamigni, L. Pure Appl. Chem. 2001, 73, (3), 421. Tsuchiya, S. J. Am. Chem. Soc. 1999, 121, 48. Davis, W. B.; Ratner, M. A.; Wasielewski, M. R. Chem. Phys. 2002, 281, 333.

63 6. Thamyongkit, P.; Yu, L.; Padmaja, K.; Jiao, J.; Bocian, D. F.; Lindsey, J. S. J. Org.

Chem. 2006, 71, ((3)), 1156. 7. Qureshi, F. M.; Martin, S. J.; Long, X.; Bradley, D. D. C.; Henari, F. Z.; Blau, W. J.;

Smith, E. C.; Wang, C. H.; Kar, A. K.; Anderson, H. L. Chem. Phys. 1998, 231, 87. 8. El-Khouly, M. E.; Gadde, S.; Deviprasad, G. R.; Fujitsuka, M.; Ito, O.; D'Souza, F.

J.Porphyrins Phthalocyanines 2003, 7, 1. 9. Wang, Q.; Campbell, W. M.; Bonfantani, E. E.; Jolley, K. W.; Officer, D. L.; Walsh,

P. J.; Gordon, K.; Humphry-Baker, R.; Nazeeruddin, M. K.; Gratzel, M. J. Phys. Chem. B 2005, 109, 15397. 10. Kalyanasundaram, K.; Vlachopoulos, N.; Krishnan, V.; Monnier, A.; Gratzel, M. J.

Phys. Chem. 1987, 91, 2342. 11. Gouterman, M., In The Porphyrins, Dolphin, D., Ed. Ed. Academic Press: New York:

1978; Vol. 3A, p 1. 12. 857. 13. 14. 15. Rodriguez, J.; Kirmaier, C.; Holten, D. J. Am. Chem. Soc. 1989, 111, 6500. Kalyanasundaram, K.; Neumann-Spallart, M. J. Phys. Chem. 1982, 86, 5163. Kalyanasundaram, K., Photochemistry of Polypyridine and Porphirin Complexes. Zamyatin, A. V.; Soldatova, A. V.; Rodgers, M. A. J. Inog.Chim.Acta 2006, 360 (3),

Academic Press: London: 1992. 16. 384. 17. 1298. 18. Karolczak, J.; Kowalska, D.; Lukaszewicz, A.; Maciejewski, A.; Steer, R. P. J. Phys. Liu, X.; Yeow, E. K. L.; Velate, S.; Steer, R. P. Phys. Chem. Chem. Phys. 2006, 8, Gurzadyan, G. G.; Tran-Thi, T.-H.; Gustavsson, T. J. Chem. Phys. 1998, 108, (2),

Chem. A. 2004, 108(21), 4570.

64 19. 20. Antipas, A.; Gouterman, M. J. Am. Chem. Soc. 1983, 105, 4896. Drain, C. M.; Kirmaier, C.; Medforth, C. J.; Nurco, D. J.; Smith, K. M.; Holten, D. J.

Phys. Chem. 1996, 100, 11984. 21. Drain, C. M.; Gentemann, S.; Roberts, J. A.; Nelson, N. Y.; Medforth, C. J.; Jia, S. L.;

Simpson, M. C.; Smith, K. M.; Fajer, J.; Shelnutt, J. A.; Holten, D. J. Am. Chem. Soc. 1998, 120, (15), 3781. 22. 23. 24. 25. Rodriguez, J.; Holten, D. J. Chem. Phys. 1989, 91, (6), 3525. Rodriguez, J.; Kirmaier, C.; Holten, D. J. Chem. Phys. 1991, 94, 6020. Kobayashi, T.; Straub, K. D.; Rentzepis, P. M. Photochem. Photobiol. 1979, 29, 925. Chirvonyi, V. S.; Dzhagarov, B. M.; Timinskii, Y. V.; Gurinovich, G. P. Chem. Phys.

Lett. 1980, 70, 79. 26. 27. 28. Kim, D. H.; Kirmaier, C.; Holten, D. Chem. Phys. 1983, 75, 305. Kim, D. H.; Holten, D. Chem. Phys. Lett. 1983, 98, 584. Chikisev, A. Y.; Kamalov, V. F.; Korteev, N. I.; Kvach, V. V.; Shkvrinov, A. P.;

Toluetaev, B. N. Chem. Phys. Lett. 1988, 144, 90. 29. Soldatova, A. V.; Kim, J.; Peng, X.; Rosa, A.; Ricciardi, G.; Kenny, M. E.; Rodgers,

M. A. J. Inog.Chem 2007, 46, 2080. 30. Gunaratne, T. C.; Gusev, A. V.; Peng, X.; Rosa, A.; Ricciardi, G.; Baerends, E. J.;

Rizzoli, C.; Kenney, M. E.; Rodgers, M. A. J. J. Phys. Chem. A 2005, 109, 2078. 31. 32. Rosa, A.; Ricciardi, G.; Baerends, E. J. J. Phys. Chem. A 2006, 110, 5180. Rosa, A.; Ricciardi, G.; Baerends, E. J.; Romeo, A.; Scolaro, L. M. J. Phys. Chem. A

2003, 107, 11468. 33. 34. Gouterman, M. J. Mol. Spectrosc. 1961, 6, 138. Rogers, J. E.; Nguyen, K. A.; D. C. Hufnagle; D. G. McLean; Su, W.; M.Gossett, K.;

Burke, A. R.; A.Vinogradov, S.; Pachter, R.; Fleitz, P. A. J. Phys. Chem. A 2003, 107, 11331.

65 35. 36. Rosa, A.; Baerends, E. J. Inog.Chem 1994, 33, 584. Soldatova, A. V.; Kim, J.; A., R.; Ricciardi, G.; E., K. M.; Rodgers, M. A. J.

submitted for publication, 2007. 37. Rosa, A.; Ricciardi, G.; Baerends, E. J.; van Gisbergen, S. J. A. J. Phys. Chem. A

2001, 105, 3311. 38. Rosa, A.; Ricciardi, G.; Baerends, E. J.; van Gisbergen, S. J. A. Coord. Chem. Rev.

2002, 5, 230. 39. 40. 41. 42. 43. Vangberg, T.; Lie, R.; Ghosh, A. J. Am. Chem. Soc. 2002, 124, 8122. Canters, G. W. J. Chem. Phys 1981, 74, (1), 157. Nguyen, K. A.; Pachter, R. J. Chem. Phys 2001, 114, (24), 10757. Nguyen, K. A.; Pachter, R. J. Chem. Phys 2003, 118, (13), 5802. Rosa, A.; Ricciardi, G.; Baerends, E. J.; Zimin, M.; Rodgers, M. A. J.; Matsumoto, S.;

Ono, N. Inog.Chem 2005, 44, (19), 6609. 44. 45. Strickler, S. J.; Berg, R. A. J. Chem. Phys. 1962, 37, 814. Cohen, B.; Crespo-Hernandez, C. E.; Kohler, B. Faraday Discuss

2004, 127, 137. 46. Dietzek, B.; Kiefer, W.; Hermann, G.; Popp, J.; Schmitt, M. J. Phys. Chem. B 2006,

110, 4399. 47. Dietzek, B.; Maksimenka, R.; Siebert, T.; Birckner, E.; Kiefer, W.; Popp, J.;

Hermann, G.; Schmitt, M. Chemical Physics Letters 2004, 397, 110. 48. Retsek, J. L.; Gentemann, S.; Medforth, C. J.; Smith, E. C.; Chirvony, V. S.; Fajer, J.;

Holten, D. J. Phys. Chem. B 2000, 104, 6690. 49. Yu, H. Z.; Baskin, J. S.; Steiger, B.; Wan, C. Z.; Anson, F. C.; Zewail, A. H. Chem.

Phys. Lett. 1998, 293, 1.

66 50. Retsek, J. L.; Medforth, C. J.; Nurco, D. J.; Gentemann, S.; Chirvony, V. S.; Smith,

K. M.; Holten, D. J. Phys. Chem. B. 2001, 105, (27), 6396. 51. Eom, H. S.; Jeoung, S. C.; Kim, D.; Ha, J.-H.; Kim, Y.-R. J. Phys. Chem. A.

1997, 101, (20), 3661.

67 CHAPTER 4: THE PHOTOPHYSICAL BEHAVIOR OF OPEN-SHELL FIRST-ROW TRANSITION METAL TETRAPHENYLTETRABENZOPORPHYRINS: COPPER AND COBALT

Abstract The ground and excited state properties of Co()TPTBP and Cu()TPTBP have been investigated by a combination of DFT/TDDFT and transient absorption spectrometry in order to draw a complete picture of the excited state deactivation. Cu() and Co() were chosen to investigate the impact from the half-filled d orbitals on the photophysical properties of the porphyrin macrocycle. For Co()TPTBP, the first observed transient which is a localized triplet state was converted to a hot d,d state, wherein intramolecular cooling occurred that was completed within 3 ps. After cooling the d,d state decayed into the ground state in an exponential manner having a 17 ps lifetime. Similar to Co()TPTBP, the first observed transient in Cu()TPTBP was assigned to the triplet state that equilibrate with an LMCT state; ground state repopulation occurred via a lower lying LMCT state. The dependence of the observed lifetime on solvent polarity confirmed the participation of the LMCT state in the overall deactivation process. The repopulation was completed within 500 ps. Investigating the photophysical behavior of the cobalt and copper complexes proved useful to highlight the relationship between the central metal on the rates of the deactivation pathways.

68 Introduction Transition metal centers in tetrapyrrolic systems can introduce d orbitals at energies within the HOMO-LUMO gap, giving rise to ligand metal charge transfer (CT), metal ligand CT and/or dd excited states at energies between that of the lowest excited * state and the ground state, helping the deactivation of the photo-excited state. Copper() and Cobalt() porphyrins have been a subject of many investigations because of their unusual photophysical properties which stem from the interaction of the half-filled d orbital with a electronic system of the porphyrin ring. As a result of coupling, the ground and singlet excited states 1(,*) become doublet 2S(*),where as the excited triplet state 3(,*) is split into a trip-doublet, 2T1(*) and a trip-quartet, 4T1(*) which lie very close in energy to each other.1, 2 The energy separation (E) between the two triplet states depend on the d- exchange integral and the small energy gap can lead to establishment of equilibrium between those two states.3 Cu has a d9 configuration with an unpaired electron on the dx2-y2 orbital. As a result the excited singlet states of the porphyrin are quenched by the paramagnetic d9 Cu() ion leading to very rapid intersystem crossing to low-energy trip-multiplet states.4 The excited state relaxation process in Cu porphyrins has been extensively studied by picosecond transient absorption and found that the rate of intersystem crossing occurs with the lifetime of <350 fs, thereby obviating porphyrin fluorescence.5, 6 Calculations have shown that in Cu complexes the half-filled dx2-y2 orbital lies within the HOMO-LUMO gap giving rise to many charge transfer transitions.7 Interaction between the filled dz2 metal orbital and the empty eg* porphyrin orbitals creates a low-lying metal to ring (d,*) charge transfer excited state and interaction between the half filled dx2-y2 metal orbital and the filled a2u porphyrin orbital creates a low-lying ring-to-metal (,d) CT state. These charge transfer states can lie between the singlet and triplet manifold.4, 8

69 In many cases, these charge transfer states are higher in energy than the set of triplets, as shown by the absence of any experimental spectral evidence during the excited state decay. However, in some cases this state can become accessible thermally or by changing the solvent polarity resulting shorter lifetimes. Transient absorption measurements on copper() porphyrins in coordinating solvents (oxygen or nitrogen containing solvents) have shown that the excited state lifetimes are reduced from nanosecond scale to picosecond scale.1, 9, 10 Kim and et al1 suggested when an axial ligand is attached to a square-planar species to make five-coordinated complex, ring-tometal charge transfer lowers the energy closer to or below the triplet manifold upon the formation of the exciplex and it acts as a strong quencher of the 2T-4T manifold, thereby shortening the lifetime.11, 12 Co() porphyrins have a d7 electronic configuration with the unpaired electron in a dz2 orbital. The ground state of these molecules are doublet while the lowest excited states are doublets and quartets, formed by the interaction of the unpaired electron with the porphyrin system.13 Iterative extended Hckel calculations predicted the participation of a charge transfer state, a2u()Co(dz2), in the deactivation process.2 This was supported by ultrafast transient absorption experiments8, 13 and near-IR absorption spectra. Picosecond kinetic studies of Co()octaethylporphyrin (OEP) and Co()tetraphenylporphyrin (TPP) in different solvents have been studied by Tait and et al13 who suggested that in non-coordinating solvents, the excited-state relaxation of the complex proceeds via the trip-doublet, 2T(*), and the 2(,d) charge transfer (CT) states with a lifetime less than 35 ps. These proposed states are doublets without any changes in multiplicity and this may be accounted for the short lifetimes observed. The determination of d-orbital energies and low-lying excited states from ESR data on cobalt() porphyrins indicate that several d,d states14 lie below the 2T1(*) state and the

70 lowest charge transfer state and might participate in the excited state deactivation process.15 In this case it seems that CT states are deactivated through lower-lying dd states. Lopponow et al15 reported a 12 ps lifetime for excited states of Co(OEP) and a class of donor-appended Co()OEP molecules and suggested that the observed transient is not the charge transfer state, but rather a dd excited state. This chapter describes the photophysical properties of the tetraphenyltetrabenzoporphyrins with Cu() and Co() as central metals. The relaxation dynamics of the excited states have been investigated by ultrafast transient absorption spectrometry and the results compared with DFT/TDDFT calculations of the nature and energies of the excited states. The properties of the quartet excited states, which involve spinflip (SF) transitions have been studied using a TDDFT formalism based on the non-collinear representation of the exchange-correlation (XC) potential,16, 17 recently implemented in the Amsterdam Density Functional (ADF) code.18

Theoretical characterization of Co()TPTBP and Cu()TPTBP Ground State Molecular Structure Analysis DFT calculations in the spin unrestricted formalism, of the Co() and Cu() analogs showed that these compounds adopt a D2d saddle conformation (Figure 4.1).

Figure 4.1. Side view of the DFT optimized molecular structure of M()TPTBP, M = Cu or Co

71 Table 4.1 summarizes the optimized bond lengths, bond angles and geometrical parameters for the two complexes. The dihedral angle between the adjacent pyrrolic nitrogen (CNNC)ad that defines the saddling of macrocycle is ~25o and the twisting of the mesophenyl groups relative to the porphyrin core (the porphyrin-phenyl dihedral angle), (C2C1CmesoC) is ~ 700 in both complexes in support of the above confirmation. parameter M Np C N C C C C C Cm Cm Co Co Co C Cmeso Cmeso C1 C1 C2 C2 C3 C3 C4 CNC NCC CCmesoC C2C1CmesoC (CNNC)op (CNNC)adb
a

Co()TPTBP 1.938 1.385 1.455 1.414 1.405 1.391 1.405 1.397 1.495 1.402 1.396 1.397 107.5o 109.3o 122.1 70.8 0o 26.9o

Cu()TPTBP 2.005 1.377 1.459 1.417 1.404 1.391 1.404 1.404 1.494 1.402 1.396 1.397 108.6o 109.0 123.3 67.2 0o 25.0

Geometry optimization was performed using all electrons basis set. The unpaired electron in

Co()TPTBP is on the dz2 (23a1) orbital; in Cu()TPTBP, it is on the dx2-y2 (23b2). bDihedral angle (deg) between adjacent pyrrole ring planes.

Table 4.1. Selected bond lengths () and bond angles (deg) calculated for M()TPTBP in the saddled D2d conformation.a

72 The difference in the central metal has a significant effect on the metal-pyrrolic nitrogen distance. The distance is larger in Cu than Co, Co-Np(1.938Ao) < Cu-Np (2.005Ao). Correspondingly, the CNC angle is larger indicating expansion of the macrocycle core because of the single occupancy of the Cu dx2-y2 orbital. The electron in this orbital is involved in bonding with the nitrogen lone pairs of the pyrrolic rings. In order to relieve electrostatic interaction, the Cu-Np distance increases, as a result of which the macrocycle expands.

Ground State Electronic Structure Analysis The ground state one electron levels obtained from the spin-restricted calculations are shown in Figure 4.2 for Co() and Cu(). The data for Ni() also included for the comparison purpose. Atomic population analysis is given in Appendix A.
-1.5 -2.0 -2.5 -3.0 -3.5
E/eV
dx -y
2 2

17a2 23b2 40e 40e 23b2 40e

-4.0 -4.5 -5.0 -5.5 -6.0

dz
2

23b2 18b1 39e 22b2 23a1 17b1 38e 16a2 18b1 22b2 39e 38e 16a2 23a1 39e 38e 16a2 23a1 18b1 22b2

CoTPTBP

NiTPTBP

CuTPTBP

Figure 4.2. Energy level diagram for Co-, Ni- and CuTPTBP. Orbital energies are obtained from spin-restricted calculations. In the numbering of the MOs, the core electrons (C, N, O, 1s; Co, Ni, Cu 1s-2p) are not included. HOMO,HOMO-1 and LUMO are depicted in red.

73 a) Relative HOMO and LUMO positions The highest fully occupied molecular orbital for all three complexes is 18b1, which is a purely macrocycle orbital having contribution mainly from the C and C. A small stabilization of the HOMO can be seen going from Co() to Cu(). It is possible that this is due to the enlargement of the macrocycle cavity by Cu that results in an increased distance between the two C on the pyrrolic rings. In Co()TPTBP, this distance is equal to 2.234 Ao, while in the Cu()TPTBP complex it is 2.238 Ao. As can be visualized in the contour plots in Figures 4.3 and 4.4, the electron densities on the -carbons in the G-HOMO (18b1) are alternating in sign. Thus, due to the expansion of the macrocycle cavity in the Cu complex the overlap between the C 2pz orbitals diminishes, decreasing the antibonding interaction which, in turn, causes the lowering of the energy of the G-HOMO. A similar effect has been seen in a comparable series of MNc(OMe)8 complexes (Nc = naphthalocyanine).19 The HOMO -1 is the 22b2 orbital where the electron density is mainly localized on the pyrrolic nitrogen atoms and the meso-carbon atoms. The G-LUMOs are the degenerate 40e orbitals that have contributions from Cmeso, C, C and N orbitals. Moving along the series Co-Ni-Cu, the energy of the LUMOs experiences a small downward shift as the size of the d orbital decreases. As seen from Tables in Appendix A, there is a small contribution to 40e from the 3d orbitals in Co (similar to the Ni analog) while the contribution of the 3d metal orbital to the LUMO in Cu()TPTBP is zero (Appendix A). The interaction between this d orbital and the system is anti-bonding as inferred from the contour plots.20 Thus smaller orbitals have lesser overlap with the orbital, lowering the energy of the resulting molecular orbital. The stabilization of the LUMOs is greater than the downward shift of the HOMOs leading to decrease the HOMO-LUMO gap causing the red shift of the Q band in the ground state absorption spectra going along the series.

74

-2.0 -2.5 -3.0 -3.5 -4.0

22b2 23b2 18b1 40e:xz 40e:yz

23b2 40e

E/eV

18b1
23a1

-4.5
39e 23a1 22b2 17b1
39e:xz 39e:yz

-5.0 -5.5 -6.0

17b1

38e
16a2

16a2

38e:xz

38e:yz

Figure 4.3. Energy level scheme for Co()TPTBP together with contour plots of orbitals.

-2.5 -3.0 -3.5 -4.0

17a2

17a2

40e
23b2

40e:xz

40e:yz

23b2

E/eV

-4.5 -5.0 -5.5

18b1

18b1
22b2

39e:xz

39e:yz

22b2
23a1

39e 38e
16a2

-6.0 -6.5

23a1
38e:xz 38e:yz

16a2

Figure 4.4. Energy level scheme for Cu()TPTBP together with contour plots of orbitals.

75 b) The metal d levels The molecular orbitals that have significant contribution from the central metal are 23b2(dx2-y2), 39e(d), 23a1(dz2) and 17b1(dxy). The 23b2 orbital, lies between the HOMO and the LUMO in the Ni and Cu complexes, while with Co center, it is above. The Cu complex has an unpaired electron in 23b2, an orbital that is mainly composed of the 3d(dx2-y2) orbital and the 2px orbitals of the pyrrolic nitrogen atoms. According to figure 4.2, the metal orbitals show stabilization when moving from Co() to Cu(). It is more obvious for the 23b2 orbital, which becomes occupied with an unpaired electron in Cu(). The empty 23b2 orbital in the Co() complex lies above the LUMO. This MO arises from the antibonding interaction between the empty metal dx2-y2 orbital and the lone pairs of pyrrolic nitrogens. The contour plots in Figure 4.3 and 4.4 clearly show that the dz2 orbital in Co()TPTBP and Ni()TPTBP is mainly a pure metal orbital (82%), with some (8%) 4s character. But in Cu()TPTBP, this orbital mixes better with the macrocycle orbital (only 2%) due to the close proximity of the interacting orbitals in energy and thus it is stabilized more.

c) Spin unrestricted calculations In recognition of the fact that both the Co(d7) and Cu(d9) complexes have doublet ground states, spin-unrestricted DFT calculations were carried out to ascertain the open shell effects. Figure 4.5 shows the molecular orbital energy level diagram obtained from spin unrestricted calculations for both Co() and Cu() compounds. The calculations indicate that the highly delocalized macrocycle orbital senses little exchange effect and the splitting between the spin up and spin down configurations is very small. However, the orbitals that are localized on the metal experience considerable splitting. For the Co() complex the largest splitting occurs in 23a1 and in the Cu() complex it happens in 23b2, both being singly occupied molecular orbitals (SOMO).

76

-2.0 -2.5 -3.0 -3.5

E/eV
56% dx -y
2 2

23b2

61% dx -y
2

23b2

40e

-4.0 -4.5 -5.0 -5.5 -6.0

18b1 22b2 39e 3% d 92% dxy 17b1 38e 16a2 23a1 8% dz
SOMO
2

23a1

86% dz 18b1

39e 63% d 22b2 17b1 92% dxy

spin

spin

-1 -2 -3
E/eV
17a2

40e

23b2 46% dx -y
2

-4
21% dx -y 23b 2
2 2

18b1 3% dxy 13% dxy 22b 2 5% d 4% d 16a2 39e 8% d 23a1 16a2 38e 5% d

-5 -6

spin

spin

Figure 4.5. The energy level diagram obtained from spin unrestricted calculations for Co()TPTBP(upper) and Cu()TPTBP(lower). According to the DFT results, the unpaired electron resides on the 23a1 in Co complex, which is mainly a pure d orbital (82% 3dz2) with some 8% 4s character. Figure 4.6

77 displays the electron density distribution in the 23a1 orbital in Co()TPTBP(left) and the 23b2 orbital Cu()TPTBP (right). Analysis of the electron density distribution in the Co complex indicates that the spin density is mostly on the cobalt atom, with small pockets of opposite spin on the Np atoms.

Figure: 4.6. The 23a1 orbital in Co()TPTBP(left) and the 23b2 orbital Cu()TPTBP(right).

In Cu()TPTBP, 23b2 becomes singly occupied. The spin density in the complex is almost equally distributed between the copper atom and the pyrrolic nitrogens. The metal levels are significantly stabilized going from the cobalt to the copper complex, attributable to the increased nuclear charge of the metal; as a result, there are no metal states in the upper valence region, apart from 23b2.

Excited States and Ground State Absorption Spectra Ground State Absorption Spectra Figure 4.7 shows the normalized ground state absorption spectra of Cu()TPTBP in toluene and Co()TPTBP in hexane. The absorption spectrum of Ni()TPTBP in toluene is also presented for comparison. Since Co()TPTBP proved not to be stable in toluene, all the experiments on this compound were carried out in hexane.

78

Normalized absorbance

1.0

637nm 643nm 648nm

1.0 0.8 0.6 0.4 0.2 0.0 550

Normalized absorbance

0.8 0.6 0.4 0.2 0.0 300

Co Ni Cu

600

650

700

wavelength/nm

400

500

600

700

wavelength/nm

Figure 4.7. Normalized ground state absorption spectra of M()TPTBP complexes with M = Cu, Ni in toluene and Co in hexane. Inset: normalized absorption in the Q band region.

The Q band corresponds to the macrocycles lowest (,*) excited state with a weak vibrational progression to the blue; the intense B band corresponds to the transition to the second excited state. The position of the B and Q bands were shifted to lower energy going from the Co to the Cu complex. Similar red shifts of the Q band have been observed with metallo-octabutoxynaphthalocyanines along the Co, Ni, Cu series. 21, 22 Table 4.2 shows the calculated vertical excitation energies and oscillator strengths for the optically allowed Q band of the Co and Cu variants with Ni23 for comparison. Also listed are the experimental values for the Q band absorption maxima.

79 TDDFT state Eva(eV/nm) f 2 CoTPTBP 4E 1.95/639 0.212 b 1 NiTPTBP 1E 1.94/640 0.210 2 CuTPTBP 4E 1.92/648 0.216 a in toluene solution, this work, bdata taken from ref 24. expa eV/nm 1.94/640 1.93/643 1.92/648

Table 4.2 Calculated vertical excitation energies (Eva) and oscillator strengths (f) for the optically allowed excited states of MTPTBP (M = Co(II), Ni(II), and Cu(II)) in the D2d confirmation and compared to experimental data.

The Q band is assigned to the 42E state in both Co and Cu complexes based on the substantial oscillator strength. The TDDFT calculations reproduce the red shift of the Q band in the series Co-Ni- Cu complexes. A bathchromic shift is consistent with stabilization of the G-LUMO relative to the G-HOMO along the series, caused by the reducing contribution of the Ni and Cu d metal orbitals to the G-LUMO.(Appendix A)

Excited States Below the S1(,*) State The rates of return to the ground state of photo-excited compounds such as those investigated here are critically determined by the nature and energies of the states lying below the photo-produced state. To assist understanding the excited state deactivation, the manifold of states lying between the Q state and the ground state has been examined by TDDFT calculations. Vertical absorption energies (Eva) related to the Frank-Condon transition from the ground state are listed in Tables 4.3 and 4.4 for the Co- and CuTPTBP complexes, respectively. Figure 4.8 shows the theoretically predicted dark states lying below the Q state for both Co and Cu complexes.

80
2.0 1.8 1.6 1.4
E/eV
2

2 A2 3E 1 A2
2 2 2

S1

2 A2 4E
4 4

3E

S1 4E
4

T1

2 B1 1 B2 1E
2 2 2

1 A2 T1

T1/ T1 1 A1
2

1.2 1.0 0.8 0.6 0.4

1 A2

1 B1 Co()TPTBP Cu()TPTBP

Figure 4.8. The theoretically predicted dark states lying below Q state for both Co and Cu complexes. The d,d states are indicated by green lines, the LMCT states are indicated by red lines, and the states. The Co() and Cu() complexes have an abundance of states of doublet and quartet multiplicity between the Q state (42E) and the ground state surface. In the Co() complex there are six excited states that lie vertically between the 2S1(,*) and the 2,4T1(,*) states (22E/ 34E) that in turn lie vertically above the ground state. They are 22A2, 24A2, 32E, 44E, 12A2, 14A2. The 44E has pure (d,d) character while others have LMCT character. 32E state has very little d character as it involves a transition out of the 38e orbital which has only 3% contribution from Co-3d.

81 statea 42E(2S1) 22A2 24A2 3E 4E 12A2 1 A2 32E (2T1) 24E (4T1) 24B1
B

compositiona (%) 18b1 40e (38) 18b1 40e (43) 16a2 23a1 (99) 16a2 23a1 (100) 38e 23a1 (99) 39e 23b2 (98) 18b1 23b2 (99) 18b1 23b2 (99) 18b1 40e (52) 18b1 40e (47) 18b1 40e (99) 17b1 23a1 (99) 22b2 23a1 (99) 39e 23a1 (99)

type ,* LMCT LMCT LMCT/d,dz2 d,dx2-y2 LMCT LMCT ,* ,* dxy,dz2 LMCT d,dz2

Evab 1.95(0.2118) 1.94 1.93 1.82 1.77 1.63 1.62 1.58(0.0003) 1.57 1.40 1.00(0.0003) 0.81(0.0003)

2 4

1 B2
B

12E
2
B

1 B1 18b1 23a1 (99) LMCT 0.46 The numbering and composition of the excited states refer to TDDFT calculations in the gas

phase; boscillator strengths in parentheses; ccomputed at the geometry optimized in the gasphase (D2d symmetry) Table 4.3. Excitation energies (eV), composition and character of the lowest excited states of Co()TPTBP. There are several pure d,d states lying below the 2,4T1(,*) set, one being 12E at 0.81 eV. The lowest LMCT states involves the transition from G-HOMO to 23a1 which has 86% contribution from metal dz2 orbital and can be considered as having some d character. For the Cu() complex, four LMCT states are seen between the Q state (42E) and ground state in addition to the 2,4T1(,*) states (12E / 14E) that lie vertically at ~ 1.5 eV. Represented are two nearly degenerate 2,4LMCT states (32E and 44E) described as the 39e 23b2 and two pairs of states lying below the T1 states. These LMCT states arise from excitation from the GHOMO (18b1) and G-HOMO-1 (22b2) to the empty Cu dx2-y2 spin orbital.

82 statea 42E(2S1) 32E 44E 12E (2T1) 14E(4T1) 1 A1

2

compositiona (%) 18b1 40e (25) 18b1 40e (23) 39e 23b2 (81) 39e 23b2 (94) 18b1 40e (53) 18b1 40e (45) 18b1 40e (99) 22b2 23b2 (99)

type ,* LMCT LMCT ,* ,* LMCT

Evab 1.91 (0.216) 1.88(0.019) 1.86 1.53 (0.004) 1.53 1.24

12A2 18b1 23b2 (100) LMCT 0.75 a The numbering and composition of the excited states refer to TDDFT calculations in the gas phase; boscillator strengths in parentheses; ccomputed at the geometry optimized in the gasphase (D2d symmetry) Table 4.4. Excitation energies (eV), composition and character of the lowest excited states of CuTPTBP. Transient Absorption Experiments: Spectral Observations and Dynamic Properties Co()TPTBP in Hexane As with the other metal-centered analogs, excitation at 400 nm directly generates the S2(,*) excited state, whereas excitation at 640 nm directly generates the lowest S1 (,*) excited state. A series of absorption spectra of a solution of Co()TPTBP in hexane (7.4 M) recorded over 40 ps after 400 nm (B band) excitation is shown in Figure 4.9. The characteristic spectral features of these absorption spectra include (i) two immediatelyformed negative absorption bands with peaks at 437 nm and 640 nm, (ii) immediate formation of positive absorption bands in the 350-400 nm, 480-580 nm, and 680-750 nm ranges and (iii) the delayed growth of positive absorption near 450nm and 650 nm.

83
0.06 0.04 0.02 0.00
41.17 ps 29.57 ps 21.21 ps 16.54 ps 11.34 ps 8.35 ps 5.43 ps 4.03 ps 3.36 ps 2.89 ps 2.59 ps

-0.02 -0.04 -0.06 -0.08 -0.10 -0.12 -0.14

350 400 450 500 550 600 650 700 750 800

wavelength/nm

Figure 4.9. Transient absorption behavior of Co()TPTBP in hexane (7.4 M), excited at 400 nm. The probe continuum was generated in a CaF2 plate.

The first observed transient (FOT), the 2.59 ps spectrum, shows a broad featureless positive band across the whole spectral window interrupted by two negative peaks in the regions covered by the intense B and Q bands of the ground state. Significant spectral changes are seen as time evolves, the early positive and negative bands diminish, and the positive absorbances at the red edges of the negative regions undergo blue shifts over several picoseconds. Subsequently all features returned to zero amplitude as ground state recovery occurred. To ascertain whether the results of B band excitation (400 nm) were different from Q band excitation and to obtain further information about decay dynamics, the compound was excited by light pulses at 635 nm. In addition, the data were collected using a probe continuum generated in a sapphire plate, which has the advantage of providing better signalto-noise at the expense of spectral coverage in the B band region. Figure 4.10 shows the evolution with time of the induced absorption spectra. The LH panel shows the first 4 ps and the RH panel shows the remainder. No significant differences in spectral shape and temporal

84 evolution could be discerned to those found with B band excitation, indicating no excitation wavelength dependence and the internal conversion is extremely rapid and complete within the instrument response (ca 200 fs). In the LH panel, the blue shift of the positive signal to the red of the Q band is clearly revealed. At ca 5 ps the spectrum has a derivative-like shape. As seen in the RH panel, this derivative spectrum decays with time showing no further wavelength shifts. It has the characteristics of a d,d spectrum as observed in many tetrapyrroles, such as the nominally planar nickel porphyrins.5, 25, 26

2 0 normalized A -2 -4 -6 -8 600
4.2 ps 2.8 ps 2.1 ps 1.8 ps 1.5 ps
A_640 nm

0.02 0.00
0.00 -0.02 -0.04 -0.06 -0.08 -0.10 -0.12 -0.14 0 10 20 30 40 time/ps 50 60 70 80
1= 1.46 0.04 ps (31%) 2= 22.570.17 ps (69%)

-0.02 -0.04 -0.06 -0.08

5.6 ps 8.4 ps 12.7 ps 16.8 ps 23 ps

550 575 600 625 650 675 700 725 750 wavelength/nm

625

650 675 700 wavelength/nm

725

750

Figure 4.10. Two time regimes of the transient absorption spectra of Co()TPTBP in hexane (8.1 M) excited at 635 nm. Left: Transient absorption evolution during the first four picoseconds of the experiment. Inset: the decay kinetics at 640 nm after 400 nm excitation. Right: Transient absorption spectra at later time.

Figure 4.11 shows kinetic profiles of the Co()TPTBP transient absorption in hexane solution time profiles at 500 nm and 680 nm probe wavelengths. The former is in the spectral region between the bleached B and Q bands; the latter is on the red side of the Q band.

85 The time profiles of the Co()TPTBP transient absorption signal at all wavelengths were fitted best by a pair of exponentials, the shortest lifetime of which showed significant wavelength dependence. Similar kinetic behavior for the decay of the excited states has also been observed for other Ni-centered tetrapyrroles.5, 26, 27 Note that at the bluer wavelength the first lifetime is ca one half of that at 680 nm, but the slower phase has the same lifetimes. Also it is evident that at 680 nm the time-dependent blue spectral shift contributes to the rising edge of the time profile and has an apparent lifetime of near 400 fs.

0.04

0.020

A_500nm

0.03

0.02

3 = 16.57 0.50 ps (15%)

A_680nm

2 = 0.99 0.01 ps (85%)

0.015

1= 0.40 0.04 ps (100%) 2= 2.10 0.08 ps (64%) 3= 16.70 0.40 ps (36%)

0.010

0.01

0.005

0.00 0 10 20 30 40 50 60

0.000 0 5 10 15 20 25 30 35 40 45 50 55 60

time/ps

time/ps

Figure 4.11. Kinetic profiles of the transient absorption signal at 500 nm (left) and 680 nm (right) probe wavelengths of Co()TPTBP in hexane after 635 nm excitation.

The time profiles shown in above figures indicate that there are two phases in the relaxation of the FOT to the ground state, the earlier one of which (ca 2.2 ps lifetime) is accompanied by wavelength shifts and results in the readily identified difference spectrum of a d,d state (Figure 4.10). This state decays into the ground state in an exponential manner (17 ps lifetime), with no further wavelength dependence and no spectral shifts, indicating that it lacks vibrational excitation. The TDDFT calculations (Table 4.2) show that there are two d,d states lying below the triplet state (1.57 eV) being a (d,dz2), 12E as the lowest, situated 0.81eV vertically above the ground state with the same multiplicity as the ground state. This

86 state arises from the transition from the anti-bonding 39e molecular orbital with 60% on the d metal character to the empty dz2 spin orbital. It is not unreasonable to assign the observed d,d state having a 17 ps lifetime, to the 12E. In Ni()porphyrins and phthalocyanines, d,d states have been reported with lifetimes in the hundreds of picoseconds region,27-29 but these states in Co porphyrins and octabutoxypthalocyanines have been reported as having lifetimes below 20 ps.22, 30 The presence of an abundance of lower-lying d,d and LMCT states (Table 4.2) and an unpaired electron probably all contribute to this rapid rate of decay. It is readily apparent in Figures 4.9 and 4.10 that the conversion of the FOT into the vibrationally cold d,d state over a few picoseconds is accompanied by significant spectral blue shifting. This is apparent at both the B and Q bands of the ground state absorption (Figure 4.8). This is symptomatic of a cooling process within the electronic envelope and has been seen in ultrafast studies of metallophthalocyanines and metalloporphyrins in this laboratory and elsewhere.5, 23, 26, 31, 32 To make for clearer argument about the nature of the FOT and subsequent species two of the spectra are presented again in Figure 4.12. It shows two of the spectra extracted from Figure 4.8; the blue curve is immediately post pulse (labeled 2 ps) and the red one is at 3 ps later.
0.04 0.02 0.00

5.0 ps
-0.02 -0.04 -0.06 -0.08 -0.10 -0.12 -0.14 350 400 450 500 550 600 650 700 750 800

2.0 ps

wavelength/nm

Figure 4.12. Spectra recorded immediately after a laser pulse at 400 nm (blue curve) and at 3 ps later (red curve) in Co(II)TPTBP in hexane.

87 This latter is the characteristic spectrum of the cooled d,d state and the former is the FOT. The FOT, except for the superposed bleaching bands, is broad and featureless and shows no resemblance to that of a d,d state. Rather it is reminiscent of the optical absorption spectrum of a (,*) state (cf the Cu complex). One such state listed in Table 4.3 is the Q state (42E) which is the one populated by Q band absorption. The other listings are the 2,4T1 pair just short of 1.6 eV above the ground state. Since no stimulated emission was observed unlike the case of the Ni23 complex, it is most likely that the FOT is one or both of the 2,4T1 pair. Presumably within a very short time this crosses into the higher regions of the d,d vibrational manifold wherein intramolecular cooling occurs and is complete within 3 ps. As vibrationally hot molecular species relax to the lower reaches of the vibrational ladder, their low energy transitions at the red edge of their optical absorption spectrum diminish while the higher energy transitions at the blue edge increase. Thus the higher energy (blue) part of the white probe beam monitors vibrationally cooler species, where the density of lower-lying vibrational states is less than the red-absorbing region. Thus it is not surprising that lifetimes at the blue edge of transient spectra are longer than at the red edge, as seen here. Similar effects have been seen in the Ni analog.23

Cu()TPTBP in Toluene A series of absorption spectra of Cu()TPTBP in toluene (2.8 M) recorded over 120 ps after 640 nm (Q band) excitation is shown in Figure 4.13. The first observed transition (FOT) (at 2 ps) displays a broad positive absorption band across the spectral window with a superimposed negative band with a minimum at 652 nm coincident with the Q band of the ground state. As the time delay between pump and probe was increased, the intensity of the transient absorption signal decreased, but no spectral changes in shape were detected.

88

0.05

0.00
121.11 ps 86.86 ps 69.04 ps 53.89 ps 40.63 ps 28.87 ps 20.57 ps 15.64 ps 11.77 ps 6.99 ps 5.13 ps 3.20 ps 2.10 ps

-0.05
0.00

-0.15

-0.10

-0.05

-0.10

B C D E F G H I J K L M N 660 670 680 690 700 710 720

wavelength/nm

500

550

600

650

700

750

800

wavelength/nm

Figure 4.13. Temporal evolution of the transient absorption spectra of Cu()TPTBP in toluene (2.8 M), excited at 640 nm. The inset shows an enlargement of the region near 675 nm. Scrutiny of Figure 4.13 and in particular, the inset thereto reveals that, unlike the Co and Ni23 cases, there is no hint of spectral blue shifts in the early picoseconds; in fact at 675 nm and at 450 nm there are clean isosbestic points. It is also clear, within the spectral window limitations that the same positive to negative switching is occurring in both Q and B band regions.

Cu(II)TPTBP in Benzonitrile Figure 4.14 shows the spectral changes induced in a solution of the Cu complex in benzonitrile (2.9 M) after 640 nm excitation. The spectral images replicate those seen in Figure 4.13.

89

0.05

0.00
72.97 ps 54.63 ps 38.25 ps 27.21 ps 17.76 ps 12.03 ps 8.13 ps 5.01 ps 2.20 ps

-0.05

-0.10

-0.15 500 550 600 650 700 wavelength/nm 750 800

Figure 4.14. Evolution of the absorption spectra of Cu()TPTBP in benzonitrile, after excitation at 640 nm.

A time profile of the repopulation dynamics at 653 nm presented in Figure 4.15 LH panel, reveals that ground state recovery occurs in a single exponential process with a lifetime of 54.0 ps. Within the regions of positive absorption the majority of the total decay had the same lifetime as the ground state repopulation signal, however, there was an additional small component that grew and decayed within the instrument response (e.g. Figure 4.15, RH panel).

90

0.00

0.08

-0.05

0.06

1= 6.20 0.29 ps (11%) 2= 53.1 0.24 ps (89%)

A_653nm

A_494nm

1 = 54.0 0.13 ps
-0.10

0.04

0.02

-0.15 0 50 100 150 200 250

0.00 0 100 200 300 400 500

time/ps

time/ps

Figure 4.15. Time profiles of the transient absorption signal at two probe wavelengths for Cu()TPTBP in toluene after photoexcitation at 640 nm.

Figure 4.16 shows the comparison of the dynamics of the ground state repopulation process of Cu()TPTBP in the solvents toluene and benzonitrile.

0.0
benzonitrile~ 34ps

normalised A_653nm

-0.2 -0.4 -0.6 -0.8 -1.0 0 50

toluene~ 54 ps

Toluene Benzonitrile
100 time/ps 150 200

Figure 4.16. Normalized kinetic profiles of the transient absorption signal at 653 nm for Cu()TPTBP in two different solvents after 640 nm excitation.

The optical difference spectra shown in Figures 4.13 and 4.14 for the Cu complex in toluene and benzonitrile, respectively, reveal that the FOT has positive absorption values

91 throughout the spectral window, superimposed on which are regions of intense negative absorption caused by bleaching of the ground state absorption. And also those two figures reveal that as the FOT (near 2 ps) decays the spectral shape does not change; in fact there are distinct isosbestic points at 450 and 675 nm. During the decay period the negative absorption is replenished with a lifetime of 54 ps (Figure 4.15, LH panel) in a single exponential process. These observations would indicate that the FOT is converting into the ground state of the complex in a one-step process. Nowhere during the spectral evolution are indications of spectral blue shifts or spectral narrowing that accompany vibrational cooling. Thus it would seem that the FOT is the unique precursor of the ground state in the deactivation scheme. However, the temporal profile in Figure 4.15, RH panel, does not support of this conclusion. This shows that the decay profile at 494 nm (and other wavelengths, not shown) is a composite of two exponential components, one having 6 ps lifetime (11%); the other (89%) a 53 ps lifetime that is coincident with the ground state recovery lifetime. It appears then, that there are two kinetically distinct populations of the FOT, both spectrally identical. It is to be noted that there is no corresponding 6 ps component of ground state recovery. It is possible that the resolution of this paradox is that the FOT (yet unassigned) becomes involved in a rapid reversible reaction with another state that lies close by energy. In such case the 6 ps lifetime component would be the decay of the initially produced FOT into the equilibrium state and the 53 ps lifetime process would be the decay of the equilibrium state into the ground state.33 An essential requirement for this scheme to be in accord with the experimental observations is for the equilibrium state to have an absorption spectrum that is indistinguishable from that of the FOT, i.e. the partner state contributes negligibly to the total absorbance within the experimental spectral window. In this condition it is the temporal

92 profile of the precursor state (here the FOT) that tracks the kinetics of the equilibrium rise and decay. With this discussion in mind it is appropriate to turn to a consideration of the state identities. In Table 4.4 the energies, composition and character of the lowest-lying states of Cu(II)TPTBP are listed, as generated by the unrestricted TDDFT calculations. The highest lying state of (,*) character is 42E at 1.91 eV with a high oscillator strength. This is the Q state and it is the state that is generated directly by the 640 nm pump pulse. The only other states of (, *) character below the Q state are the 12E/14E degenerate pair at 1.53 eV. For this lower-lying localized states to be the FOT requires that the
2

T conversion (formally an internal conversion) could be accomplished within the

instrument response function (ca 200 fs). This has been described for various Cu() porphyrins and the conversion to the triplet state from the Q state is greatly enhanced by the presence of the unpaired electron.34 Table 4.4 reports that there is a pair of LMCT state lies adiabatically between the 2S(*) and the 2T1(*) that can facilitate the internal conversion. In support of this is the fact that no stimulated emission was observed post-pulse, hence no emissive states (e.g. 2S1) were present in the sample post-pulse, as would be the case if all 2S1 had indeed collapsed into 12E within the pulse duration. So, the transient observed at the delay time of 2ps (FOT) is assigned to the porphyrin triplet states. As seen in Table 4.4, there is a LMCT state lies close in energy to the pair of triplet states and that can be in equilibrium with those triplet states and 6 ps lifetime component would be the decay of the initially produced FOT into the equilibrium LMCT state. Figure 4.15 shows that the process of repopulation of the ground state (LH panel) has the same lifetime as the decay of the equilibrium state (53 ps). This, together with the appearance of the spectral isosbestic behavior would imply that the equilibrium state returns to the ground state without the intrusion of intervening species, OR, that the intervening

93 species have lifetimes much shorter than the equilibrium state and therefore the rate of loss of the equilibrium state is the rate determining process in the repopulation of the ground state. The energy gap from the 12E/14E pair to the ground state is ca 1.2 eV and the rate of the direct process would most certainly be very much lower than the 54 ps lifetime measured here. The latter is the explanation favored here, because a direct, rapid radiationless transition between the Q and ground states is unfavorable because the 1.91 eV energy difference would lead to very small Franck-Condon overlaps, and if it happened the resulting ground state would be vibrationally very hot and no indications of vibrational cooling (cf Co complex) were observed. On the other hand, (Table 4.4) there is another LMCT state lies at 0.75 eV. Thus it is concluded that the equilibrated state proceeds through even the lower lying state of LMCT character in a cascade with all the intermediate species having ephemeral existence. In support it is noted that Chen et al35 reported that in a derivative of CuTBP (copper meso-tetrakis(p-methoxyphenyl)tetrabenzoporphyrin-CuTMPTBP) relaxation to the ground state occurred with a 50 ps lifetime, but no details of intervening states were offered. In benzonitrile solution (Figure 4.16), the repopulation of the ground state is more rapid with a lifetime of ca 34 ps. The close proximity of these LMCT states to the ground state would expect to shorten the lifetime in comparison with the 54 ps lifetime in toluene. This supports the notion that LMCT states are involved in the deactivation pathway, since in high dielectric media LMCT states move to lower energies, aiding the deactivation.

Summary and Conclusions The excited state spectral and dynamic behavior of Co()TPTBP and Cu()TPTBP has been investigated using transient absorption spectrometry with femtosecond time resolution and DFT/TDDFT computational methods. Figure 4.17 summarizes the mechanism of excited state deactivation pathways for both Co()TPTBP and Cu()TPTBP complexes.

94
2

S1

S1

T1/4T1

>200 fs

T1/4T1

>200 fs

LMCT

6 ps 2 ps 50 ps
2

S0

15-20 ps

S0
LMCT

Reaction coordinate

Reaction coordinate

Figure 4.17. Proposed schematic diagrams for the excited state relaxation pathways of Co()TPTBP (LH panel) and Cu()TPTBP (RH panel).

For both complexes, it was found that the internal conversion from B band excitation to S1 state is extremely rapid. For Co()TPTBP, the FOT as recognized as the localized triplet state which is next converted to the vibrationally hot d,d state. It converted to cool d d,d state over a few picoseconds accompanied by significant spectral blue shifting. d,d state decayed into the ground state in an exponential manner having 17 ps lifetime. In Cu()TPTBP, ground state repopulation occurred through the set of (, *) triplet states via a lower lying set of LMCT states.

References 1. 2. Kim, D.; Holten, D.; Gouterman, M. J. Am. Chem. Soc. 1984, 106, 2793. Antipas, A.; Gouterman, M. J. Am. Chem. Soc. 1983, 105, 4896.

95 3. Kalyanasundaram, K., In Photochemistry of Polypyridine and Porphyrin Complexes,

Academic Press: San Diego, CA: 1992. 4. 4373. 5. 6. Rodriguez, J.; Kirmaier, C.; Holten, D. J. Am. Chem. Soc. 1989, 111, 6500. Kruglik, S. G.; Apanasevich, P. A.; Chirvony, V. S.; Kvach, V. V.; Orlovich, V. A. J. de Paula, J. C.; Walters, A. V.; Jackson, A. B.; Cardozo, K. J. Phys. Chem 1995, 99,

Phys. Chem 1995, 99, 2978. 7. Antipas, A.; Dolphin, D.; Gouterman, M.; Johnson, E. C. J. Am. Chem. Soc. 1978,

100, 7705. 8. Yu, H. Z.; Baskin, J. S.; Steiger, B.; Wan, C. Z.; Anson, F. C.; Zewail, A. H. Chem.

Phys. Lett. 1998, 293, 1. 9. 10. Yan, X.; Holten, D. J. Phys. Chem 1988, 92, 5982. Holten, D.; Gouterman, M. In Optical Properties and Structure of Tetrapyrroles,

Blauer, G.; Sund, H., Eds. Walter de Gruyter, Berlin, New York: 1985; p 63. 11. 12. 13. 14. 15. Jeoung, S. C.; Takeuchi, S.; Tahara, T.; Kim, D. Chem. Phys. Lett 1999, 309, 369. Jeoung, S. C.; Kim, D.; Cho, W. D.; Yoon, M. J. Phys. Chem 1996, 100, 3075. Tait, C. D.; Holten, D.; Gouteman, M. J. Am. Chem. Soc. 1984, 106, 6653. Lin, W. C. Inog. Chem 1976, 15, (5), 1114. Loppnow, G. R.; Melamed, D.; Leheny, A. R.; Hamilton, A. D.; Spiro, T. G. J. Phys.

Chem 1993, 97, 8969. 16. 17. 18. 19. 20. Wang, F.; Ziegler, T. J. Chem. Phys. 2005, 122, 074109. Wang, F.; Ziegler, T. J. Chem. Phys. 2004, 121, 12191.

Davis, W. B.; Ratner, M. A.; Wasielewski, M. R. Chem. Phys. 2002, 281, 333.
Ricciardi, G.; Soldatova, A. V.; Rosa, A. J. Inog. Bio 2008, 102, (3), 406. Rosa, A.; Baerends, E. J. Inog.Chem 1999, 33, 584.

96 21. 22. Rosa, A.; Baerends, E. J. Inog.Chem 1994, 33, 584. Soldatova, A. V.; Kim, J.; A., R.; Ricciardi, G.; E., K. M.; Rodgers, M. A. J.

submitted for publication, 2007. 23. 857. 24. Zamyatin, A. V.; Soldatova, A. V.; Rodgers, M. A. J. Inog.Chim.Acta 2006, 360, (3), Zamyatin, A. V.; Soldatova, A. V.; Rodgers, M. A. J. Inog.Chim.Acta 2006, 360 (3),

857-868. 25. 26. 27. Rodriguez, J.; Holten, D. J. Chem. Phys. 1989, 91, (6), 3525. Rodriguez, J.; Kirmaier, C.; Holten, D. J. Chem. Phys. 1991, 94, 6020. Rosa, A.; Ricciardi, G.; Baerends, E. J.; Zimin, M.; Rodgers, M. A. J.; Matsumoto, S.;

Ono, N. Inog.Chem 2005, 44, (19), 6609. 28. 29. 30. 8969. 31. Gunaratne, T. C.; Gusev, A. V.; Peng, X.; Rosa, A.; Ricciardi, G.; Baerends, E. J.; Kim, D. H.; Holten, D. Chem. Phys. Lett. 1983, 98, 584. Kim, D. H.; Kirmaier, C.; Holten, D. Chem. Phys. 1983, 75, 305. Loppnow, G. R.; Melmed, D.; Leheny, A. R.; Hamilton, A. D.; Spiro, T. G. 1993, 97,

Rizzoli, C.; Kenney, M. E.; Rodgers, M. A. J. J. Phys. Chem. A 2005, 109, 2078. 32. Soldatova, A. V.; Kim, J.; Peng, X.; Rosa, A.; Ricciardi, G.; Kenny, M. E.; Rodgers,

M. A. J. Inog.Chem 2007, 46, 2080. 33. Hoshino, M.; Nagamori, T.; Seki, H.; Chihara, T.; Tase, T.; Wakatsuki, Y. J. Phys.

Chem. A 1998, 102, 1297. 34. 35. Soldatova, A. V. Bowling Green State University, Bowling Green, 2007. Chen, P.; Tomov, I. V.; Dvornikov, A. S.; Nakashima, M.; Roach, J. F.; Alabran, D.

M.; Rentzepis, P. M. J. Phys. Chem. A 1996, 100, 17507.

97 CHAPTER 5: THE PHOTOPHYSICAL PROPERTIES OF CHROMIUM() AND MANGANESE() TETRAPHENYLTETRABENZOPORPHYRINS: AN INSIGHT INTO EXCITED STATE DECAY DYNAMICS Abstract The photophysics of Cr()TPTBPCl and Mn()TPTBPCl have been investigated using transient absorption spectrometry to provide data necessary for understanding the influences that metals with partially occupied d orbitals have on the photophysical properties of the porphyrin macrocycle. After 640 nm excitation in Cr()TPTBPCl, the S1 state undergoes fast intersystem crossing (4S14T1), within a very short period of time (ca.0.05 ps lifetime) to 4T1 state. The 4T1 state of Cr()TPTBPCl in toluene deactivated with a lifetime of 224 ps, resulting the
4

T1 6T1 equilibrium. In benzonitrile solution Cr()TPTBPCl showed a lifetime of 90 ps to

result the above mentioned equilibrium. A substantial decrease in the lifetimes of photoexcited Cr()TPTBPCl in benzonitrile indicated the possible existence of a CT state that acts as a quenching state of the trip-multiplet state. In Mn()TPTBPCl , the excited sing-quintet, 5S1(,*) state deactivated to the triplet trip-quintet, 5T1(,*) within the instrument response time. Within short time period afterwards, it generated a hot d,d state wherein cooling occurred within 4 ps. Subsequently the cooled d,d state repopulated the ground state with a 120 ps lifetime. It showed the same kinetics in both coordinating and non coordinating solvents indicating that no CT states were involved in the deactivation process. Neither Cr()TPTBPCl nor Mn()TPTBPCl showed emission at room temperature.

98 Introduction Chromium() and Manganese() porphyrin complexes are of considerable interest for several reasons. Foremost is that they show unique absorption spectra, most probably due to the unusual electronic structure induced by half filled metal d orbitals. Cr() and Mn () are classified as d- type hyper porphyrins with paramagnetic metal ions with stable lower oxidation states.1 Both Manganese() and Chromium() porphyrin complexes have been studied for photonic and optoelectronic materials.2 Although chromium() porphyrins are not naturally occurring substances in biological systems, their chemical and photochemical properties have been widely studied in relation to their photoinduced axial ligand dissociation and association reactions.3-5 Such studies can provide information related to the biological functions of axial ligands in heme proteins.6 The Cr() metal ion has a d3 (S=3/2) electronic configuration with half-filled dxy, dyz and dxz orbitals and empty dx2-y2 and dz2 orbitals. As a result of coupling between the porphyrin and metal electronic configurations, the ground and singlet excited 1(,*) states become quartet 4S(,*), where as the excited triplet 3(,*) is split into trip-doublet 2T(,*), trip-quartet 4T(,*) and trip-sextet 6T(,*) states. In addition intramolecular CT transitions between porphyrin and metal d orbitals and d,d transitions within the metal orbitals are also prossible.7 Gouterman et al. reported that there were two luminescence bands at 815 nm and 850 nm from ClCr()TPP at 77K, and those bands were assigned to the emission originated from trip-quartet 4T(,*) and trip-sextet 6T(,*) states. They also showed that the quartet and sextet states to be in thermal equilibrium.8 Photophysical studies on Cr porphyrins have carried out to elucidate the photodissociation mechanism of the axial ligand. Hoshino et al. reported laser flash photolysis of ClCr()TPP(L) (L= sixth axial ligand) in various solvents and suggested that the 4S1(,*)

99 excited state acts as the main route for the photodissociation process.3-5, 9-11 Jeoung et al. also studied the photo-dissociation of halochromium() tetraphenylporphyrin using transient absorption and Resonance Raman Investigations and explained the phenomenon in terms of electron density changes in the metal d orbitals, which is sensitive to the interaction with donor axial ligands.12 They found that the temporal evolutions of photoinduced absorption and bleaching signals of XCr()TPP in benzene exhibit biphasic decay profiles with time constants of 1 and 20 ms. The faster decay was assigned to the four coordinated CrTPP* species and the slower decay component to the recombination process returning to the original five-coordinate XCr()TPP species. A significant reduction in the lifetime of photoexcited ClCr()TPP in THF was observed as compared with that in benzene. An investigation on the luminescent properties of Cr() porphyrins showed that the lifetime of the photo-excited state is relatively short ~295 ps in ethanol and also depends on the solvent.13 Manganese porphyrin complexes serve as model compounds for the manganese dependent oxygen evolution in green plant photosynthesis.14 As a basis for understanding their possible role in photosynthesis, many studies have carried out on the photochemistry of manganese porphyrins.15-17 The Mn() metal ion has a high spin d4 ground state electronic configuration(S= 2) and only the high energy dx2-y2 orbital is unoccupied in the ground state. Because of the coupling of the unpaired metal electrons with the ring electrons, the ground state is a quintet (5S0). The quintet excited state (5S0) is derived from the lowest excited ring (,*) singlet and the trip-multiplet (3T1, 5T1, 7T1 ) set is derived from the lowest ring (,*) triplet.7 According to Hunds rule the lowest energy state have the highest multiplicity. Mn() porphyrins are generally considered as non-luminescent. This is usually attributed to quenching of the normally emissive (,*) excited states by CT or d,d states at a

100 lower energy. 1, 7, 18 Irvine et al.19 used 1-ps excitation at 597 nm with Mn()TPPCl in CH2Cl2 and pyridine and reported a 17 ps lifetime for the decay of the strong absorption near 500 nm; Chirovonyl and et al 20 measured a 55 ps lifetime for Mn()Meso(Cl) in the 450600 nm region following photoexcitation. Both the above time constants were assigned to the decay of a ring (,*) trip-multiplet state. Holten et al reported the kinetics of the transient absorption in the 500-900 nm region using Mn()TPPCl and Mn()OEPCl in CH2Cl2 and pyridine and reported two transients having fast and slower components. The fast decay had 5-30 ps lifetime and they mentioned that Chirovonyls values is an average for the slow and fast components that they have observed with Mn()OEPCl. For the slower component Holten reported an 80 ps lifetime for TPP and 140 ps lifetime for OEP and they assigned the short-lived component to the trip-quintet 5T1(,*), a fraction of which relaxes to the longer lived trip-septet, 7T1(,*). They also suggested that the decays of both trip-multiplets proceeds via lower energy CT or d,d excited states.21 There is a scarcity of quantum chemical studies on manganese porphyrins and there are so many unresolved questions to be answered, such as how the unpaired electron spins are distributed in the different electronic states.22, 23 Gunter et al has mentioned that the experimental chemistry of manganese porphyrins greatly needs theoretical support to interpret the experimental data.24 Figure 5.1.displays the orbital energy levels for Cr() and Mn() porphyrin complexes with trivalent metal chlorides by iterative extended Hckel calculations.

101

-7 -8 orbital energy/eV -9 -10 -11 -12

dx -y
2

dx -y
2

eg(*) d dxy a2u a1u Cr

111

eg(*) d dxy a1u Mn

111

a2u

Figure 5.1. Orbital energy levels for Cr and Mn porphyrin complexes with trivalent metal chlorides by iterative extended Hckel calculations. Data for the figure are taken from reference 8.

The figure shows that the dz2 orbital in Cr() is vacant and half filled in Mn(). The half filled dxy, dyz and dxz orbitals are located between the LUMO and HOMO of the porphyrin ring whereas an empty dx2-y2 orbital lies well above the eg orbital giving rise to CT(d*,d) or d,d state that would participate in the deactivation of photo-excited Cr(III) and Mn() porphyrins.

PHOTOPHYSICAL PROPERTIES OF Cr()TPTBPCl Ground State Absorption Spectra Figure 5.2 shows the normalized ground state absorption of Cr()TPTBPCl in different solvents to show the effect of coordinating solvent vs. non-coordinating solvents. Toluene and DMF serve as non-coordinating solvents while benzonitrile is a coordinating solvent.

102

1.0
A_normalized to B band

1.0
toluene benzonitrile
A_normalized to B band

0.8 0.6 0.4 0.2 0.0 300

0.8 0.6 0.4 0.2 0.0 300

toluene DMF

400

500

600

700

400

500

600

700

800

wavelength/nm

wavelength/nm

Figure 5.2. Normalized ground state absorption of Cr()TPTBPCl in toluene, DMF and benzonitrile solutions.

Cr()TPTBPCl showed strong B band absorptions near 500 nm, and a Q band absorption in the 600-700 nm region. These main bands can be allocated to transitions a1u(), a2u() eg(*). In addition there are other bands in the region between 350 nm to 450 nm. For metal atoms with partly filled d orbitals, allowed charge transfer transitions a1u(), a2u() eg(d) are also expected and they might be account for the extra bands seen near 400 nm. The B band absorption maximum in toluene becomes slightly red-shifted in benzonitrile solution. The absorption spectra in toluene and DMF showed no difference. Iterative extended Hckel calculations performed by Gouterman8 showed that the energy gap between the metal d orbitals and the a2u orbital decreases along the series of transition metals Cr(), Mn() and Fe() (Figure 5.1). As a consequence, CT transitions from the ground state; a1u(), a2u() eg(d) become more favorable along this series. The energy of this CT state is higher than that of the B band for Cr(), and the additional absorption peaks of Cr()TPTBPCl in toluene and benzonitrile to the blue of the B band can be assigned to those CT transitions.

103 Transient Absorption: Spectral Observations and Dynamic Properties of Cr()TPTBPCl Femtosecond transient absorption spectrometry with excitation wavelength in the Q and B band regions was employed in order to explore the influence of the central metal on the excited state deactivation. Different spectra were measured using different solvents.

Cr()TPTBPCl in toluene and DMF Figure 5.3 displays the overlaid transient absorption spectra of Cr()TPTBPCl in toluene at different time delays following 640 nm excitation. To ascertain whether the results of Q band excitation were different from B band excitation and to obtain further information about decay dynamics, the compound was excited by light at 400 nm, which generates the 4S2 (,*) state, whereas excitation at 640 nm produced the 4S1 (,*). Transient spectra of both excitations showed that there is no difference proving that internal conversion from S2 S1 is fast.
0.05 0.00 -0.05

0.05 0.00 -0.05

-0.10
A

-0.15 -0.20 -0.25 -0.30 -0.35 500 550

2.61 ps 83.18 ps 294.30 ps 776.30 ps

-0.10
A

-0.15 -0.20 -0.25 -0.30 -0.35

2.90 ps 3.94 ps 24.50 ps 161.14 ps 459.73 ps 1155.73 ps

600

650

700

750

500

550

600

650

700

750

wavelength/nm

wavelength/nm

Figure 5.3. Left: Transient absorption spectra of Cr()TPTBPCl in Toluene, excited at 400 nm. Right: Transient absorption spectra of Cr()TPTBPCl in DMF, excited at 640 nm.

104 The first observed transient (ca.2 ps) displays the characteristic features of the excited states localized on the porphyrin macrocycle, exhibiting a broad positive absorption band with maximum at 530 nm and two negative bands at 495 nm and 665 nm due to ground state depopulation. When the time delay between the pump and probe was further increased, the intensity was decreased having the same spectral shape. Two isosbestic points, 515 nm and 680 nm were maintained. Figure 5.3, RH panel displays the evolution of transient absorption spectra of Cr()TPTBPCl in DMF solution after excitation in the Q band. Transient absorption spectra in DMF replicate the spectral images those seen in Figure 5.3 in toluene showing that the broad positive absorption interrupted by two negative bands at 495 nm and 665 nm. It also shows the small changes in intensity of the signal at early evolution time and as the time evolves the signal decreased without changing spectral shape. In Figure 5.4 the LH panel displays the temporal decay profile taken at 530 nm excited at 640 nm in toluene solution. The RH panel shows the time profile at the same wavelength during the first 5 ps. On the same figure the time profile of a Raman signal generated from the solvent is superimposed to show the instrument response profile. The experimental time window limits the observation range and the kinetic profile at 530 nm showed a bi-exponential fit having 0.05 ps and 224 ps lifetimes.

105

0.07 0.06 0.05

A_530nm
1 = 0.05 0.01 ps (23%) 2 = 224.47 2.53 ps (77%)

1.0 0.8 0.6 0.4 0.2 0.0 solvent

0.05 ps

A_530nm

0.04 0.03 0.02 0.01 0.00 -0.01 0 200

400

600 time/ps

800

1000

4 time/ps

Figure 5.4. Left: kinetic behavior of Cr()TPTBPCl in toluene at 530 nm after 640 nm excitation. Right: first 6 ps of kinetic trace at 530 nm upon excitation at 640 nm. The dashed blue curve is the instrument response to a solvent Raman signal. Both curves are normalized to unity.

It has been reported that for various Cu() porphyrins and phthalocyanines the intersystem crossing from the S1 state to the T1 state occurs very rapidly (<350 fs), followed by the establishment of the trip-doublet/trip-quartet equilibrium.25, 26 Presumably, the interaction between the excited porphyrin ligand and paramagnetic central copper might be shortening the lifetime of the 2S1 state. It has also known that the paramagnetic Cr()TPP complex does not show normal (, *) fluorescence and that extremely weak emission from
4

T1 is observed in ethanol.13 These findings were interpreted as arising from extremely rapid

intersystem crossing from 4S1 to 4T1. Moreover, excitation to any quartet excited state should lead to rapid radiationless relaxation to the lowest excited state quartet, 4T1.8 Considering the time profile in Figure 5.4, the short lifetime ~ 0.05 ps can be assigned to the conversion from (4S14T1) that generates the -localized triplet state.

106 The energy gap (E) separating the 4T1 and 6T1 trip-multiplet state is ca.550 cm-1, and it could result in equilibration between the 4T1 6T1 states.13 The same study by Harriman demonstrated that 4T1 state of ClCrTPP in hexane deactivates with a lifetime of 295 ps, resulting the above mentioned equilibrium. The slower lifetime in figure 5.4 can be assigned to the 4T1 state of the ClCrTPTBP which is in equilibrium with 6T1 states.

Cr()TPTBPCl in Benzonitrile In Figure 5.5 the upper panel shows the temporal evolution of a solution of Cr()TPTBPCl in benzonitrile following 640 nm excitation. The lower panel shows spectral cuts taken from early time evolution in toluene and benzonitrile solution excited at 640 nm to display the blue shift of spectra in toluene solution.

1
0.05 0.00
A

0 -1 -2
2.23 ps

-0.05 -0.10 -0.15 -0.20 -0.25 500 550 600 650 700 750 800 wavelength/nm 3.67 ps 21.59 ps 82.38 ps 228.29 ps 660.38 ps 1404.23 ps
A

-3 -4 -5 -6 -7 -8 500 550 600

2.61 ps

benzonitrile toluene

650

700

750

wavelength/nm

Figure 5.5. Left: Transient absorption spectra of Cr()TPTBPCl in benzonitrile solution following 640 nm excitation. Right: The early time evolution of Cr()TPTBPCl in benzonitrile and toluene solutions normalized to the maximum positive band.

107 Similar to the spectral profiles in DMF and Toluene, Cr()TPTBPCl in benzonitrile shows the characteristic features of excited states localized on the porphyrin macrocycle, with a broad positive absorption interrupted by the Q band bleaching. It has a positive maximum at 537 nm interrupted by two negative peaks at 505 nm and 669 nm. Figure 5.6 displays the kinetics of Cr()TPTBPCl in benzonitrile solution at 535 nm following 640 nm excitation.

0.08

0.06
A_535nm

0.04

2 =

0.29 0.03ps (19%)

0.02

1 = 83.97 1.87ps (81%)

0.00 0 25 50 75 100 time / ps 125 150

Figure 5.6.The kinetic profile of Cr()TPTBPCl in benzonitrile solution followed by the 640 nm excitation.

It also showed biexponential kinetics having 0.29 ps and 84 ps lifetimes. The short lifetime can be viewed as faster intersystem crossing process as seen in previously. When comparing the changes in spectra and kinetics in benzonitrile with toluene, there are two scenarios to consider. Firstly the slower lifetime has shortened, secondly the spectra shifted to the blue in benzonitrile. Axial ligands in Cr porphyrins are known to be anomalously labile compared with those of other chromium() complexes having non-porphyrin ligands.9, 27-29 Transient absorption and resonance Raman investigations on the axial ligand photodissociation studies of Halochromium() Tetraphenylporphyrin (XCr TPP, X=Cl, Br) in coordinating solvents such as THF have showed that the axial halogen ligand photodissociates to form the five-

108 coordinate CrTPP(THF) on photoexcitation. Significant reduction in the lifetime compared to non coordinating solvents was assigned to the five-coordinate photoexcited Cr TPP(THF)* species, which decays rapidly due to the participation of low energy states below the tripmultiplet (,*) states. Five coordinate Cr TPP(THF)* species was suggested to possess (,d) charge transfer character based on the comparison with those of other paramagnetic metalloporphyrins. With that in mind, when return to photoexcitation to the Cr()TPTBPCl in benzonitrile, the red shifted transient that has seen compare to the transient in toluene solution can also be assigned to six co-ordinated Cr()TPTBPCl(benzonitrile)* species. A substantial decrease in the lifetimes of photoexcited Cr()TPTBPCl in benzonitrile can be ascribed to the possible existence of a CT state that acts as a quenching state of the tripmultiplet state. The ground state absorption spectra of Cr()TPTBPCl in benzonitrile and toluene exhibit absorption maxima at 505 nm and 496 nm, respectively, in the Soret band region as shown in (Figure 5.2) The absorption maxima of Cr() compound in toluene and DMF showed to be no significant difference. This proposes that toluene and DMF does not affect the axial ligand nature and the ground-state electronic structure of Cr() porphyrin, whereas benzonitrile solvent acts as a -donor to form a six-coordinate Cr porphyrin (ClCrTPTBPCl(benzonitrile)), in the ground state.

PHOTOPHYSICAL PROPERTIES OF Mn()TPTBPCl Ground State Absorption Spectra Figure 5.7 displays the ground state absorption spectra of Mn()TPTBPCl in three different solvents. The absorption spectra of Mn()TPTBPCl are dissimilar to the normal absorption spectra of porphyrins in the visible region. It shows a splitting of the B band into

109 bands at 400 nm and 530 nm. The additional bands can be attributed to charge transfer bands assigned to ,d transition.

1.0
1.0 0.8 absorbance 0.6 0.4 0.2 0.0 300 390nm 532nm benzonitrile toluene 684nm
470nm

0.8

0.6
A
404nm

0.4
670nm 622nm

0.2

400

500

600

700

0.0 300

400

wavelength/nm

500 600 wavelength/nm

700

800

Figure 5.7. LH panel: Absorption spectra of Mn()TPTBPCl in toluene and benzonitrile; RH panel: Absorption spectra of Mn()TPTBPCl in DMF.

Iterative extended Hckel calculations have shown that the energy of the CT state is at approximately the same energy in Mn()TPP.19 The red ground state absorption bands in the octaalkyl substituted complexes such as Mn()OEP(Cl) had been ascribed to transitions a2u() a1g(dz2). The bands near 680 nm and 620 nm in Mn()TPPCl had been described as a representation of a CT transition.21 In addition, there may be large number of CT((,d), ( d,*)) and d,d states available which may not evident from the ground state visible spectrum. Even though the spectral pattern is the same for toluene and DMF, some of the maxima are sharpened and red shifted when going from toluene to DMF. Boucher noted the similar spectral behavior with halide complexes of the manganese() porphyrins going from benzene to chloroform and which was ascribed to a solvent effect involving the hydrogen bonding ability of the chloroform.30 The same thought can be applied the difference of the

110 porphyrins dissolve in coordinating solvent, the spectra were identical to the spectra observed with Mn()TPTBPCl in toluene and benzonitrile.14, 30

Transient Absorption: Spectral Observations and Dynamic Properties of Mn()TPTBPCl Mn()TPTBPCl in Toluene Figure 5.8 shows the overlaid transient absorption spectra at a series of delay times after 400 nm excitation of Mn()TPTBPCl in toluene solution. There can be seen strong excited-state absorptions to the blue of 500 nm, bleaching of the absorption bands in the B and Q band regions and positive absorption between 550 nm to 650 nm and from 725 nm extending to longer wavelengths. The spectrum of the first observed transient (Figure 5.9, lower panel, spectrum at 1.79 ps) has more positive absorption in the 550 to 650 nm region which is red of the Soret band and may be assigned to a trip-multiplet state. More specifically it can be assigned that the trip-quintet, 5T1(,*), based on the fact that in first row paramagnetic complexes the intersystem crossing process within localized system occurs extremely rapidly due to the presence of the unpaired electron. Moreover, Manganese() porphyrins are identified as the essentially non-luminescent which implies the Q State deactivates within the instrument response time to the triplet from the lowest sing-quintet,
5

S1(,*).

111

0.04 0.02 0.00

A

0.01 0.00
1.79 ps 2.19 ps 2.59 ps 3.23 ps 4.83 ps 8.22 ps 16.52 ps 30.32 ps 58.42 ps

-0.01
A

-0.02 -0.04 -0.06 -0.08 500 550

-0.02 -0.03 -0.04

44.62 ps 21.02 ps 15.02 ps 10.42 ps 7.62 ps 5.63 ps 4.03 ps 510 525 540 555 570

600

650

700

750

wavelength/nm

wavelength/nm

0.02 0.00 -0.02

A

-0.04 -0.06 -0.08 500 550

4.83 ps 1.79 ps

600

650

700

750

wavelength/nm

Figure 5.8. LH panel: Transient absorption spectra of Mn()TPTBPCl in toluene solution following 400 nm excitation. RH panel: spectral evolution after 4 ps in the wavelength region 500-570 nm showing decay of dd state. The lower panel shows spectral cuts taken at two time delays.

As time progressed, the positive absorption signal red of the B and Q bands shifted to the blue evolving a spectrum having a derivative like shape and no isosbestic behavior. At later times, the derivative-shaped spectrum decayed to the ground state having isosbestic points at 500 nm and 454 nm, reflecting complete ground-state recovery. Presumably within a very short time the trip-quintet, 5T1(,*) state, crosses into the higher regions of the d,d vibrational manifold (Figure 5.8, lower panel, 5 ps transient),

112 wherein intramolecular cooling occurs and is complete within 4 ps. After the cooling it repopulates the ground state. The spectral evolution described above was accompanied by complex temporal behavior with wavelength dependent lifetimes. The temporal decay profiles taken at 530 nm and 686 nm are shown in Figure 5.9.

0.00 -0.01

0.000 -0.007

-0.02
A_530nm

-0.03 -0.04 -0.05 -0.06 -0.07 0

A_686nm

3 = 0.94 0.01 ps (39%) 1 = 16.04 0.29 ps (33%) 2 = 120.53 1.71 ps (28%)

-0.014 -0.021 -0.028 -0.035

1 = 0.69 0.03 ps (23%) 3 = 13.66 0.23 ps (50%) 2 = 117.51 2.43 ps (27%)

100

200

300

400

500

150

300 wavelength/nm

450

600

wavelength/nm

Figure 5.9. Kinetic behavior of Mn()TPTBPCl in toluene solution at 530 nm and 686 nm following 400 nm excitation. The kinetics could be described with a three exponential fit throughout the spectral window implying that there are three components related to the deactivation from photoexcited Mn()TPTBPCl. The first phase is characterized by a fast decay (~ 1 ps lifetime) and it is probably the relaxation of the vibrationally hot species within the molecule (IVR), the second phase (~ 16 ps lifetime) represents thermal losses to solvent oscillators. After the vibrational cooling the d,d state deactivates to the ground state as shown by the isosbestic behavior at 500 nm and 454 nm, with a lifetime of 120 ps.

113 Mn()TPTBPCl in Benzonitrile Holten et al21 mentioned that the rapid deactivation from trip-multiplets in Mn() porphyrins probably proceeds via lower energy CT or d,d excited states. To check the possibility of involving a CT state in the deactivation process, femtosecond transient absorption studies have done in benzonitrile solution since the involvement of a charge transfer state should be sensitive to the solvent polarity. Figure 5.10 shows the spectral cuts taken from early and later times of the spectral evolution of Mn()TPTBPCl in benzonitrile solution following 400 nm excitation. It also replicates the spectral difference as seen in toluene. The first observed transient shows a broad positive absorption band to the red of the B band interrupted by bleaching of B and Q bands.

0.02 0.01 0.00 -0.01

A

-0.02 -0.03 -0.04 -0.05 -0.06 500 550 600 650 700 750 wavelength/nm 18.76 ps 3.06 ps 1.99 ps

Figure 5.10. The spectral cuts taken from early time and later times of spectral evolution of Mn()TPTBPCl in benzonitrile solution following 400 nm excitation.

Figure 5.11 shows the kinetics profiles of the transient absorption signal at different wavelengths of Mn()TPTBPCl in benzonitrile solution excited at 640 nm.

114

0.00 -0.02 -0.04

A_530nm

0.00

-0.02
1 = 0.67 0.02 ps (54%) 2 = 12.37 0.82 ps (18%) 3 = 120.75 3.72 ps (28%)

-0.06 -0.08 -0.10 -0.12 -0.14 0 100

A_688nm

-0.04

1 = 1.17 0.11 ps (24%) 2 = 15.34 0.96 ps (44%) 3 = 127.15 7.60 ps (32%)

-0.06

-0.08

200

300

400

500

100

200

300

400

500

wavelength/nm

wavelength/nm

Figure 5.11. Femtosecond kinetic profiles of the transient absorption signals of Mn()TPTBPCl in benzonitrile solution after excited at 640 nm.

The kinetics were best fitted by a three exponential decay with wavelength dependent kinetics similar to the toluene case. The slowest phase (ground state recovery) remained unchanged in benzonitrile solution with the wavelength, in support of the conjecture that the excited state deactivation occurs through a d,d state rather than a CT state. Following Kim and et al 18 there is another possible decay pathway that could be involved. The 5T1(,*) decay might give rise to the 7T1(,*). The rapid 5-20 ps decay could be viewed, in part, as the time for equilibrium of the trip-multiplets. Kim et al have rationalized the putative longer lifetime for 7T1(,*) on the basis of spin selection. Foremost, direct deactivation from the trip-septet to the quintet ground state is spin forbidden. Next, no low energy septet CT or d,d excited state to which 7T1(,*) could decay rapidly are expected. Moreover no septet d,d excited states are existent because no metal ring CT transition involving the half-filled d orbitals can lead to the septet excited state. As a result, the only possible septet CT states are 7(,dx2-y2) and these will be very high in energy and unlikely to participate in decay of 7T1(,*). With the experiments performed here related to

115 Mn()TPTBPCl, it is thought to be most likely that the deactivation occurs through the d,d state. Summary and Conclusions The excited state spectral and dynamic behavior of Mn()TPTBPCl and Cr()TPTBPCl have been investigated by transient absorption spectrometry with femtosecond time resolution in an effort to understand the paramagnetic nature on the photodeactivation. It has been found that photoexcitation of the Cr()TPTBPCl generates 4T1 state within very short period of time and the excited species deactivates resulting the 4T1 6T1 equilibrium state. It was found out that there may be possible involvement of LMCT state during the deactivation process. In the Mn()TPTBPCl, the triplets have formed during the instrument response time and forms the vibrationally hot d,d state. Cooled d,d state has decayed to the ground state. To summarize the above conclusions, a schematic diagram for the deactivation of the photoexcited Cr()TPTBPCl and Mn()TPTBPCl in toluene is depicted in Figure 5.12.
4

S1

S1

T1

>100 fs

T1

T1

>200 fs 16 ps

224 ps
4

d, d
7

T1

S0

LMCT

S0 120 ps

Reaction coordinate Reaction coordinate Figure 5.12. Proposed schematic diagram for the excited state relaxation pathways of Cr()TPTBPCl and Mn()TPTBPCl.

116 References 1. 1992. 2. Zhang, J.; Wang, D.; Shi, T. S.; Wang, B.; Sun, J.; Li, T. Thin Solid Films 1996, 284Kalyanasundaram, K. Photochemistry of Polypyridine and Porphirin Complexes,

285, 596. 3. 6095. 4. 5. 6. Inamo, M.; Nakaba, H.; Nakajima, K.; Hoshino, M. Inorg. Chem. 2000, 39, 4417. Inamo, M.; Hoshino, M. Photochem. Photobiol. 1999, 70, (4), 596. Alden, R. G.; Chavez, M. D.; Ondrias, M. R.; Courtney, S. H.; Friedman, J. M. J. Am. Inamo, M.; Eba, K.; Nakano, K.; Itoh, N.; Hoshino, M. Inorg. Chem. 2003, 42, (19),

Chem. Soc. 1990, 112, (8), 3241. 7. Gouterman, M., In The Porphyrins, Dolphin, D., Ed. Academic Press: New York:

1978; Vol. 3A, p 62. 8. 2343. 9. Hoshino, M.; Nagamori, T.; Seki, H.; Chihara, T.; Tase, T.; Wakatsuki, Y.; Inamo, M. Gouterman, M.; Hanson, L. K.; Khalil, G. E.; Leenstra, R. J. Chem. Phys 1975, 62,

J. Phys. Chem. A. 1998, 102, (8), 1297. 10. 11. Hoshino, M.; Tezuka, N.; Inamo, M. J. Phys. Chem. 1996, 100, (2), 627. Inamo, M.; Okabe, C.; Nakabayashi, T.; Nishi, N.; Hoshino, M. Chem. Phys.Lett.

2007, 445, 167. 12. 4816. 13. 14. 15. Harriman, A. J. Chem. Soc., Faraday Trans. 1982, 1, (78), 2727. Boucher, L. J. J. Am. Chem. Soc. 1970, 92, (9). Suslick, K. S.; Watson, R. A. New. J. Chem 1992, 16, 633. Jeoung, S. C.; Kim, D.; Cho, D. W.; Yoon, M. J. Phys. Chem. A. 2000, 104, (21),

117 16. 17. 18. Suslick, K. S.; Watson, R. A.; Wilson, S. R. Inorg. Chem. 1991, 30, 2311. Jeoung, S. C.; Kim, D.; Cho, D. W. J. Raman Spectrosc. 2000, 31, 319. Kim, Y.; Choi, J. R.; Yoon, M.; Furube, A.; Asahi, T.; Masuhara, H. J. Phys. Chem.

B. 2001, 105, (36), 8513. 19. Irvine, M. P.; Harrison, R. J.; Strahand, M. A.; Beddard, G. S. Ber. Bunsenges. Phys.

Chem 1985, 89, 226. 20. 21. 22. 23. Chirvonyi, V. S.; Dzhagarov, B. M. Fuusika Mat. 1982, 31, 129-132. Yan, X.; Kirmaier, C.; Holten, D. Inorg. Chem. 1986, 25, (26), 4774. Ghosh, A.; Gonzalez, E. Isr. J. Chem. 1999, 40, 1. Ghosh, A.; Vangberg, T.; Gonzalez, E.; Taylor, P. J. Porphyrins Phthalocyanines

2001, 5, 345. 24. 25. 26. 27. 28. Gunter, M. J.; Turner, P. Inorg. Chem. 1994, 33, 1406. Kim, D.; Holten, D.; Gouterman, M. J. Am. Chem. Soc. 1984, 106, 2793. Yan, X.; Holten, D. J. Phys. Chem. 1988, 92, 5982. Fleisher, E. B.; Krishnamurthy, M. J. Am. Chem. Soc. 1971, 93, 3784. Summerville, D. A.; Jones, R. D.; Hoffman, B. M.; Basolo, F. J. Am. Chem. Soc.

1977, 99, (25), 8195. 29. 932. 30. Boucher, L. J. J. Am. Chem. Soc. 1968, 90, (24). Yamaji, M.; Hama, Y.; Miyazaki, Y.; Hoshino, M. Inorganic Chemistry 1992, 31, (5),

118 CHAPTER 6: HEAVY METAL EFFECT ON THE PHOTOPHYSICAL PROPERTIES OF PLATINUM TETRAPHENYLTETRABENZOPORPHYRINS: INSIGHT FROM EXPERIMENTAL AND RELATIVISTIC DFT/TDDFT STUDIES Abstract The ultrafast photodynamics of Pt()TPTBP has been investigated and results are compared with relativistic DFT and TDDFT calculations in order to explore the heavy metal effect on the photophysics of tetrabenzoporphyrins. The Pt analog showed a blue shift of the position of the Q band compared with first-row Zn-centeredcompound. It was found that a localized S1 state undergoes fast intersystem crossing (ca.500 fs lifetime) to a triplet 3(,*) state. A low fluorescence quantum yield (0.0003) was observed and it showed a high yield of phosphorescence. The triplet state lifetime was found to be ca. 41 s significantly shorter than Zn triplet state indicating that faster intersystem crossing due to spin orbit interaction introduced by the heavy Pt atom in the third row transition series.

Introduction Pt()and Pd() porphyrins are typical members of the phosphorescent classification of porphyrins that have gained attention for use in some practical applications. The phosphorescence of those metalloporphyrins is quenched by molecular oxygen(O2) and this property has been utilized to make optical sensors to detect oxygen.1 Recent studies have reported the potential use of Pt porphyrins as photosensitizers for conversion and storage of solar energy2, and as potential molecular conductors.3 Moreover they can been used as photodynamic and photothermal sensitizers for tumor treatment because of the excitation energy of these systems can be transferred from their T1 state to ground state molecular oxygen, thereby

119 generating the chemically reactive singlet state of oxygen that can initiate oxidative damage in cellular media, including tumor cells.4 The inclusion of heavy atoms into molecular systems leads to changes in photophysical parameters due to the enhancement of inter-combination transitions, known as the heavy-atom effect. Coordination of a heavy metal atom into the system increases the rate of the intersystem crossing between singlet and triplet states of the metalloporphyrins, thereby enhancing the rate of radiative decay.5 Pt ()porphyrins have been classified as hypsoporphyrins (irregular porphyrins) as the Soret band undergo a shift to shorter wavelength (hypsochromic shift) with respect to regular metalloporphyrin systems.6 The hypsochromic shift is interpreted as the strong d (dxz,dyz) metal orbital interaction with the porphyrin eg (*)orbital (metal- to- ligand - back- bonding). This interaction increases the separation between the porphyrin HOMO and LUMO causing the electronic transitions to occur at shorter wavelengths.7 It is known that Pt() in a square planar coordination environment displayed little tendency to bind axial ligands owing to the low-spin d8 configuration in which the filled dz2 orbital repels axial ligands approaching to the metal ion.7 The Co(), Ni() (d7,d8) porphryns show no luminescence and it has been postulated that this is due to the presence of d,d states lying between the porphyrin ,* triplet and the ground states. The Pd()and Pt() porphyrins which are also d8 strongly phosphoresce implying that the d,d state lies higher in energy than the 3(,*). 8 Examination of the literature reports on Pt(), and Pd() porphyrins revealed information about the mechanism of excited state deactivation. It mainly occurs through the formation of the -localized triplet state, and the radiative processes, fluorescence and phosphorescence. Pd()porphyrins such as Pd()OEP(octaethylporphyrin) and Pd()TPP(tetraphenylporphyrin)

120 show a weak fluorescence, giving an estimated lifetime for the 1Q(,*) state of ca.20 ps. Pt()OEP showed the lifetime of S1 15 ps.9 Both Pd()and Pt()porphyrins phosphoresce strongly with quantum yields between 0.2 Pd() and 0.9 (Pt().6 Picosecond studies on Pt()TPP and Pd()TPP have shown triplet (,*) lifetimes of > 10 ns while Pt()OEP has shown a triplet lifetime of > 50 ns .10 The TBP derivative of Pt showed strong phosphorescence at 745 nm with a quantum yield 0.18 in pyridine solution. The phosphorescence spectrum and the lifetime of Pt()TBP varied with the temperature.2 The photophysical and structural properties of Pt and Pd complexes are affected by relativistic effects that dominate for elements of atomic number greater than 50. Relativistic effects on the physicochemical properties of metals have been studied widely.11,12 It has been shown that only through consideration of relativistic effect could the difference between oxidation states be explained. For example platinum exhibits both the Pt() and Pt(IV) states, the higher oxidation state in palladium is less stable than in platinum and the majority of palladium compounds involve Pd0 or Pd. 13 Non-relativistic and relativistic TDDFT calculations performed on Pt compounds proved that the larger HOMO-LUMO gap observed in heavy metal complexes can be predicted theoretically only when relativistic effects were taken into account.14 In this chapter, the photophysical properties of Pt()TPTBP are investigated by means of femtosecond and nanosecond transient absorption spectrometry. In addition relativistic DFT and TDDFT calculations have been performed to obtain the information necessary to justify the mechanism proposed by experiments. Whenever necessary, Zn, Ni and Pt metals are brought into the discussion to compare the data to have a relative picture on the photodeactivation mechanism.

121 Theoretical characterization of Pt()TPTBP: heavy metal effect Ground State Molecular Structure Analysis Relativistic density functional ground-state geometry optimization has been carried out for the Pt()TPTBP complex in order to investigate the effect of the heavy metal atom on the geometrical parameters of the macrocycle and to provide basic structures for the calculations of the excited states. Geometry optimization has shown that it adopts a D2d saddled conformation in the ground state, as is the case for the first-row transition metal complexes presented in previous chapters. Analysis of the X-ray crystallographic structure provided by Mark Thompson at USC Chemistry Department reveals the non-planar structure of Pt()TPTBP with saddle-type distortion. The optimized structure and atom labeling of Pt()TPTBP are illustrated in Figure 6.1 with atom labeling. C4 C3 C2 C1 figure 6.1. C Cmes C Pt N Cm C o

Figure 6.1. Top view (above) and side view (below) of the DFT-optimized molecular structure of Pt()TPTBP together with atom labeling.

122 Selected optimized bond lengths and angles for Pt()TPTBP obtained from calculation and x-ray data are summarized in Table 6.1. parameter MN C N C C C C C C m C m Co Co Co C Cmeso Cmeso C1 C1 C2 C2 C3 C3 C4 CNC NCC CCmesoC C2C1CmesoCa (CNNC)op (CNNC)adb
a b

Pt()TPTBPcal Pt()TPTBPx-ray 2.018 1.383 1.457 1.415 1.405 1.390 1.403 1.400 1.495 1.401 1.396 1.397 108.9o 108.6o 124.3o 71.2o 0o 21.5o 2.011 1.377 1.458 1.399 1.405 1.382 1.387 1.400 1.495 108.3o 108.9o 124.0o 71.2o 0.83o 20.1o

Dihedral angle between the phenyl group and the plane of the porphyrin ring; Dihedral angle (deg) between adjacent pyrrole ring planes.

Table 6.1. Comparison of the optimized theoretical values of the selected bond lengths () and bond angles (deg) with x-ray data for the Pt()TPTBP. To compare the changes in bond lengths and bond angles along the NiPdPt series, calculated values are given in the Table 6.2. It can be seen that the most changes occur in the porphinato nitrogen-metal bond (M-Np) distance when changing the metal from Ni to Pt. For example Ni-Np distance was 1.922 (Table 6.2), whereas in the Pt complexes this value was found to be 2.018.

123

Parameter MN C N C C C C C Cm C m Co Co Co C Cmeso Cmeso C1 C1 C2 C2 C3 C3 C4 CNC NCC CCmesoC C2C1CmesoC (CNNC)op (CNNC)ad

Ni()TPTBP 1.922 1.384 1.454 1.413 1.405 1.395 1.406 1.395 1.494 1.403 1.402 1.399 107.4o 109.4o 121.4o 70o 0o 25.2o

Pd()TPTBP 2.022 1.380 1.459 1.416 1.405 1.391 1.403 1.400 1.495 1.401 1.396 1.397 109.0o 108.6o 124.3o 70.9o 0o 22.4o

Pt()TPTBP 2.018 1.383 1.457 1.415 1.405 1.390 1.403 1.400 1.495 1.401 1.396 1.397 108.9o 108.6o 124.3o 71.20 0o 21.5o

Table 6.2. Selected Bond Distances (Ao) and Bond Angles (deg) calculated for M()TPTBP in the D2d confirmation, M = Ni, Pd, Pt.

The size of the metal ion is increasing when going from the first to the third row transition metal complexes and as a result the size of the porphyrin cavity is also increased. Due to the enlargement of the macrocycle, the dihedral angle between the C-N bonds on the adjacent pyrrole rings that defines the degree of saddling is decreased along the series Ni-Pt (from 25.2o to 21.5o respectively). It is worth noting that the Zn-Np distance is 2.047 as seen in Table 3.1. Zn has d10 electronic configuration with dx2-y2 being filled. The repulsion between nitrogen lone pairs and the d electrons causes an increase in Zn-Np compared with Pt-Np (2.018 ).

124 Ground State Electronic Structure Analysis The highest occupied and the lowest unoccupied one electron levels for the ground states of Pt()TPTBP and Pd()TPTBP in the D2d saddled confirmation are shown in Figure 6.2. The highest occupied and the lowest unoccupied levels are depicted in red to highlight the differences in the relative position of the frontier orbitals that are likely to cause changes in photophysical behavior when heavier atoms are introduced into the macrocycle cavity. The data for Ni()TPTBP are also included in the figure. The energies and percentage composition of the molecular orbitals are given in the Appendix A.
-1.5 -2.0 -2.5 -3.0 -3.5 E/eV -4.0 -4.5
2

24a2 33b2 40e dx -y

2 2

59e

63e

23b2

18b1

28b1 32b2 58e d 37a1 dz 36a1 dz

2

29b1 35b2 62e d 40a1 dz

2

22b2 -5.0 dz 23a1

-5.5 -6.0 -6.5

d 39e 38e 16a2 22a1

57e 22a2

23a2

61e 39a1 dz
2

NiTPTBP

PdTPTBP

PtTPTBP

Figure 6.2. Energy level scheme for M()TPTBP, M= Ni, Pd, Pt. (a) HOMO and LUMO relative positions The highest fully-occupied Gouterman molecular orbital in the Ni, Pd and Pt complexes is of b1 symmetry. The composition of this orbital is the same for all three metal complexes. It is a purely macrocycle orbital with large amplitude on the C, Cm and Co atoms. As can be inferred from the data in Appendix A (and Figure 6.3), the central metal has no contribution to this orbital. But Figure 6.2 reveals that going from Ni Pd Pt, there is a small stabilization in the

125 HOMO. It is possible that when a larger metal is introduced into the macrocycle, the cavity expands and the antibonding interaction between adjacent C atoms decreases resulting in the stabilization of HOMO. The lowest unoccupied Gouterman orbital in the Ni-Pd and Pt series is a pair of degenerate e orbitals. As can be seen from Appendix A (and Figure 6.3), it has larger contribution from the macrocycle ring with some contribution from pyrrolic nitrogen. It also has small contribution from the metal d orbital. The contribution from the d orbital is increased on going from Ni (3%) to Pt (5%). Going from Ni to Pd, the G- LUMO is stabilized and going from Pd to Pt, the LUMO is upshifted again. The interaction between the empty macrocycle orbital and the d orbital of the central metal is an antibonding one and it introduces the metalmacrocycle - back donation.15 In heavy metal complexes, it is more effective due to the larger and more diffuse character of the 4d and 5d metals that results in the upshift of the LUMOs.16 The central metal does not contribute to the composition of the HOMO as seen in the contour plots in Figure 6.3. But inserting an atom of larger radius into the porphyrin cavity causes an expansion of the macrocycle and a concomitant lowering of the energy of the HOMO. Moreover, the change in the position of LUMO results in the blue shift of the Q band absorption along the Ni to Pt series.

126

G-LUMO 24a2 63e:yz 63e:xz

29b1

G-HOMO

62e:yz

62e:xz

40a1-side view

35b2

40a1

61e: xy

61e: xz

23a2

39a1 Figure 6.3. Contour plots of the MOs of Pt()TPTBP.

127 (b) the metal d levels It is worth commenting on the strength of the interaction between the tetrapyrrole Np lone pairs and the metal- dx2-y2, and the out-of-plane interaction between the tetrapyrrole Np Pz and the metal-d. The relative positions of the metal d levels are determined mainly from these two influences, followed by the size of the interacting orbitals and on the size of the macrocycle cavity.17,18 In first row transition metals, the virtual dx2-y2 orbital plays an important role in the excited state deactivation since it lies very close in energy to the HOMO. Larger spin-orbit coupling in the second and third row transition metals locates the energy of the virtual dx2-y2orbital well above that of the G-LUMOs. The virtual dx2-y2orbital participates in the antibonding interaction with the pyrrolic Np lone pairs to form the 23b2 orbital in Ni()TPTBP where it is composed of 51% of the dx2-y2 orbital and 24% of the Np Px orbital. Its bonding counterpart 17b1 lies 1.8 eV below the HOMO. In Pt()TPTBP, the virtual dx2-y2 orbital lies much higher in energy. Its bonding counterpart 27b1 (composed of 76% of the dx2-y2 orbital and 4% of the Np Px) lies 2.23 eV below the HOMO. The relativistic destabilization of the 5d orbitals also allows for better metal-to-ligand back donation. Thus the unfilled dx2-y2 orbital that controls the excited state deactivation in the first row transition metal complexes is not expected to play any role in the deactivation of the optically produced S1 excited state in the second and third row metal complexes. The highest occupied metal d orbitals are the dz2 (23a1 in the Ni complex, 37a1 in the Pd complex and 40a1 in the Pt complex) and the d (39e in the Ni complex, 58e in the Pd, 62e in the Pt). The dz2 orbital in Ni()TPTBP is nearly a pure metal orbital (84% dz2), whereas in Pd()TPTBP the contribution from dz2 is 61% and in Pt()TPTBP it has a 63% dz2 contribution.

128 This shows that the dz2 orbital is stabilized by the interaction with the macrocycle when going from Zn to Pt. Metal d orbitals play a significant role when considering the out-of-plane interaction. The metal contribution to these orbitals changes as in the Ni complex, 56%, in Pd 26% and in Pt it has 33% contribution from the d bonding orbital. In the Pt complex the contribution from the metal d slightly has increased owing to the larger size of the metal 5d orbital. The spacing between the resulting bonding/antibonding pair (39e/38e in Ni and 62e/61e in Pt) is very small. These orbitals experience downward shift when going from Ni to Pd and upshifted again when going further to the Pt macrocycle, similar to the metal contribution to these orbitals. When going from Pt to Pd, the increased repulsive interaction between the metal and macrocycle orbitals results in these MOs moving to a higher level. The remaining occupied 3d orbital, the in-plane dxy orbital is an almost pure 3d orbital. In Ni()TPTBP, it is 19b2, in Pd()TPTBP it is 26b1 and in Pt()TPTBP it is 29b2. In the Pt complex the contribution from the occupied dxy metal orbital to this MO is the largest due to the more diffusive 5d orbital in Pt. The upshift of the empty dx2-y2orbital, together with the stabilization of the occupied metal-levels remove any possibility of involvement of ligand field excited states in the deactivation of the optically produced (,*) excited state in the Pt complex.

Excited States and Ground State Absorption Spectra Figure 6.4 shows the ground state absorption spectra of Pt()TPTBP together with Zn analog in toluene solution. Extinction coefficients are given for absorbance data. The extinction coefficient of Pt()TPTBP Qband with max = 615 nm is 2.02x105 M-1cm-1. The extinction

129 coefficient for Pd analogue has been reported as 1.05x105 M-1cm-1 at max = 629 nm in benzene solution.19Compared to the Q band and B band absorption maxima in the Zn complex, Pt complex showed a blue shift; where the Q band gain intensity while the B bands lose intensity. (Figure 6.4.)

6 5
x 10 (M cm )

4 3 2 1 0 300

ZnTPTBP PtTPTBP

-5

-1

-1

400

500

600

700

800

wavelength/nm

Figure 6.4. Ground state absorption spectra of M()TPTBP (M = Pt and Zn) in toluene solution. Extinction coefficients are given for absorbance data.

Table 6.3 lists the vertical absorption energies and oscillator strengths calculated for the Q band and B band and compared with experimental data for both Pt and Zn complexes in toluene. It also includes the composition of the BP/ALDA solution vectors in terms of the major one-electron MO transitions. According to the TDDFT excitation energies, the Q band on the ground state absorption spectra in Pt()TPTBP, can be assigned to the 11E state, computed at 616 nm. It has considerable oscillator strength and is mainly derived from the promotion of one

130 electron from the G-HOMO to the G-LUMO. It also has some minor contribution from HOMO1 to LUMO. TDDFT state
1 Zn()TPTBP 1 E(Q)

Exp. f 0.13 1.52 E(eV/nm) 1.90(652) 2.68(462)

Composition(%) Eva(eV/nm) 18b1 40e(71) 22b2 40e(27) 22b2 40e(59) 18b1 40e(21) 23b2 40e(11) 1.89(656) 2.62(473)

21E(B)

Pt()TPTBP

11E(Q) 21E(B)

29b1 63e(83) 35b2 63e(14) 35b2 63e(72) 29b1 63e(10)

2.016(616) 2.79(445)

0.24 2.019(615) 1.08 2.89(430)

Table 6.3. Vertical excitation energies and oscillator strengths (f) computed for the optically allowed excited states of M()TPTBP(M= Zn, Pt) responsible for the appearance of the Q band and B band and compared with experimental data.

The calculated blue shift of the Q band of the Pt complex compared to the Zn analog is in excellent agreement with the experimental data. With heavier metals, it was necessary to take into account relativistic effects in the geometry optimization process.14 Table 6.3 also reveals the increase of the HOMO-LUMO gap in the Pt complex. It can be interpreted as a result of GHOMO stabilization and destabilization of the G-LUMO due to the stronger back bonding repulsion between the Pt d orbital and the macrocycle orbital.7,20 The intense B band at 2.79 eV (445 nm) arises mainly(72%) from the one electron transition from HOMO-1 to LUMO.

131 Optically Silent Excited States Below the S1(*) State In order to provide the insights on the excited state deactivation for Pt()TPTBP subsequent to Q band excitation, the manifold of singlet and triplet symmetry forbidden states lying below the Q band were also examined. The vertical absorption energies calculated for these are summarized in Table 6.4. TDDFT state Composition(%) character Pt()TPTBP 1 1E 1 3E 29b1 63e(83) 29b1 63e (99) * * Eva 2.01 1.63

Table 6.4. Excitation energies (eV) calculated for the low-lying excited states of Pt()TPTBP The TDDFT calculations indicate that there is only one silent state lies between the Q state and the ground state. It is the emissive triplet (*) state and is doubly degenerate. It also undergoes a Jahn-Teller distortion as previously described in chapter 3.

Steady State Luminescence and Transient Absorption Experiments Steady State Luminescence Being a heavy atom, Pt influences the production of the triplet state, resulting in faster intersystem crossing through enhanced spin-orbit coupling.3 An increase in spin-orbit coupling changes the photophysical properties in such a way that can increase the phosphorescence quantum yield, decrease the fluorescence quantum yield and increase the rate constant for intersystem crossing.

132 Pt()TPTBP showed a weak fluorescence having max at 620 nm with quantum yield (F) of 0.0003 in toluene measured as outlined in chapter 2. The fluorescence spectrum of Pd()TPTBP was previously published having similar quantum yield to Pt complex. The normalized ground state absorption spectrum of Pt()TPTBP in the Q band region, the fluorescence spectrum along with the phosphorescence spectrum, excited at 442 nm in toluene solution are shown in Figure 6.5.

normalized absorbance and fluorescence

0.8

15

0.6

768

10

0.4 5

0.2

0.0 540

0 570 600 630 700 800 900

wavelength / nm

Figure 6.5. Normalized room temperature absorption (black solid line) and fluorescence spectra (red dashed line) and phosphorescence spectra (red solid line) in toluene solution. Excitation wavelength for emission spectra was 442 nm.

A small Stokes shift of 131cm-1 between the fluorescence and absorption maxima was observed. The phosphorescence spectrum of Pt()TPTBP in thoroughly degassed toluene solution showed a maximum at 768 nm at room temperature. It has been reported that in aerated solutions at room temperature the intense signal at 1270 nm can be attributed to the emission

phosphorescence intensity / V

1.0

615

620

20

133 arising from the 1g3g transition in oxygen, generated by energy transfer from triplet state precursors.21 (see later) Phosphorescence was the major emission from this porphyrin similar to what has been previously observed for Pt()tetrabenzoporphyrin (TBP)2 and Pd()TPTBP.19 Coordination of a heavy metal increases the rate of intersystem crossing between singlet and triplet states enhancing the rate of radiative decay from the triplet state.22,23 All the photophysical properties are summarized in Table 6.5 and compared with reported Pd data.

Q band/ 10-5 Qband / -9 -1 -1 fluor /nm T1 in Ar/s 10 kq/ M s F nm mM-1cm-1 Zna 30 652 47 668 0.008 236 1.2 b Pd 46 629 105 669 0.0003 195 Ptc 78 615 202 620 0.0003 42 2.26 a extinction coefficient in toluene. triplet lifetimes were measured in 1% of pyridine/toluene M()TPTBP Z solution. All the other measurements were carried out in pyridine solution;
b c

data taken from ref;19 this work; all in toluene solution.

Table 6.5. Photophysical properties of M()TPTBP (M = Zn, Pd, Pt)

The Q band maximum of the Pt complex shows a hypsochromic shift compared to Zn and Pd. In view of that the T1-S0 energy gap calculated by TDDFT (Table 6.3) is higher in the Pt complex compare to the Zn analog. The bimolecular rate constant for quenching of the T1 state by molecular oxygen (see later) is also higher with the Pt complex.

134 Transient Absorption Experiments Femtosecond Transient Absorption Femtosecond pump-probe absorption experiments were carried out to illustrate the early events that follow photoexcitation (see Figure 6.6). The LH panel shows the spectra of a solution of Pt()TPTBP in toluene solution excited at 400 nm and probed using a white light continuum pulse generated in a CaF2. plate In addition the experiment was repeated using 610 nm excitation and a probe continuum pulse generated in a sapphire plate which has the advantage of providing better signal-to-noise at the expense of spectral coverage in the B band region (see RH panel).

0.05 0.00 -0.05

A

0.2 0.1 0.0

-0.10 -0.15 -0.20

7.8 ps 4.2 ps 2.3 ps

-0.1 -0.2 -0.3 500 550 600 650

67.47 ps 21.67 ps 2.36 ps

350 400 450 500 550 600 650 700 750 wavelength / nm

700

750

800

wavelength/nm

Figure 6.6. Left: evolution of the transient absorption of Pt()TPTBP in toluene, excited at 400 nm, using a. probe continuum generated in a CaF2 plate. Right: evolution of the transient absorption of Pt()TPTBP in toluene, excited at 610 nm, white light sapphire.

Excitation at 400 nm directly generates the S2 (,*) excited state, whereas excitation at 610 nm directly generates the lowest S1 (,*) excited state. In the former case the S1 (,*)

135 excited state is expected to result from internal conversion from the S2 (,*). In fact, the early time scales in Figure 6.6 showed to be no difference between the two types of excitation, leading to the conclusion that internal conversion is extremely rapid and is complete within the instrument response (ca.200 fs). Scrutiny of Figure 6.6 shows that the first observed transition (FOT) is observed by a broad featureless positive band from 350 nm to 800 nm interrupted by negative bands at 430 nm and 615 nm in the regions of the intense B and Q bands of the ground state. By analogy to the other porphyrins studied, this spectral feature can be assigned to the S1 Sn absorption within the system. The subsequent spectral changes were minor during the first few picoseconds (Figure 6.6 LH panel) after which there were no changes (Figure 6.6 RH panel) during the time window of the ultrafast spectrometer (~1.5 ns).

0.08

1.0 0.8

0.06
A_530nm
1 = 0.40 0.07 ps
A_584nm

0.6 0.4 0.2 0.0

1 = 0.53 0.02 ps

0.04

0.02

0.00 0 2 4 6 time/ps 8 10
-0.2 1.0 1.5 2.0 2.5 3.0 3.5 time / ps 4.0 4.5 5.0

Figure 6.7. Left: kinetic profile of the Pt()TPTBP in toluene solution measured at 530 nm upon excitation at 400 nm. Right: kinetic trace at 584 nm upon excitation at 610 nm. The dashed blue curve is the instrument response to a solvent Raman signal. Both curves are normalized to unity.

136

Given the similarity of the absorption spectra between S1 and T1 observed for other metalloporphyrins studied earlier, this process can be identified as the intersystem crossing (S1T1) which generates the localized triplet. In Figure 6.7 the LH panel displays the time dependence of the photoinduced transient absorption signal at 530 nm after 400 nm excitation. The RH panel shows the time profile at 584 nm following 610 nm excitation. On the same figure the time profile of a Raman signal generated from the solvent is superimposed to show the instrument response profile. It shows that the intensity of the transient absorption signal at 584 nm decreased more slowly than the solvent response. Experimental points were fitted starting from the time when Raman signal had disappeared. A single exponential fit lead to an estimated ca.0.5 ps lifetime for the decay, which can be assigned to the intersystem crossing, S1T1, process. The LH panel also shows a single exponential fit to the decaying absorption signal at 530 nm having a lifetime of 0.5 ps. It is closely similar to the observed single exponential decay that was seen after excitation at 610 nm. The nanosecond transient absorption spectra closely resemble the ultrafast transient spectra on the longer time scale.

Nanosecond Transient Absorption Figure 6.8 displays the transient absorption spectra excited at 430 nm in Ar-saturated toluene solution at various time delays. At early times the data show a broad photoinduced positive absorption signal with a superimposed strong bleaching of the ground state absorption.

137

0.01 0.00 -0.01

A

-0.02 -0.03 -0.04 -0.05

1.5 s 5.0 s 10.0 s 15.0 s 20.0 s 30.0 s 40.0 s 50.0 s 70.0 s

400 450 500 550 600 650 700 750 wavelength / nm

Figure 6.8. Nanosecond transient absorption spectra of Pt()TPTBP in Ar-saturated toluene at different delay times followed by 430 nm excitation.

This first observed transient spectrum closely resembles the last transient on the picosecond time scale (Figure 6.6; RH panel) and as such it can be assigned to the absorption of the T1 state. These transient absorption features, both positive and negative decayed concomitantly with isosbestic points, indicating that the triplet state decayed by repopulating the ground state surface. The time profile for the Q band bleaching recovery in Ar-saturated toluene solution is shown in the upper LH panel in figure 6.9. The measured T1 lifetime was 41.7 s. In the presence of oxygen, the decay of the triplet state was enhanced, remaining single exponential. The rate constant of the decay was directly proportional to the concentration of oxygen (Figure 6.9; upper right). In air saturated solution, the lifetime was 0.5 s (lower RH panel) and in O2 saturated solution this lifetime reduced to 0.055 s.

138 Earlier experimental data on the Pd analogue19 showed triplet excited state lifetime as 195 s in de-oxygenated pyridine. This is ca.5 times longer than that obtained for Pt()TPTBP; this lifetime shortening can be presumably attributed to faster intersystem crossing due to the higher atomic number(Z) with Pt center.

0.00 -0.01
A_430nm_Ar

800

600
Ar/

-0.02
= 41.68 0.15s

400
3 -1

-0.03

200
-0.04 -0.05 0 50 100 150 200 250 300 350 400 time/s

Ksv = (93.20 2.24)*10 M

0 0 2 4 6 8 concentration of O2 / mM 10

0.000 -0.005
A_620nm_O2

0.000
A_620nm_air

-0.005

-0.010
1 = 0.054 0.0004 s

-0.010
= 0.500 0.002 s

-0.015 -0.020

-0.015

-0.020
-0.025 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

time/s

time/s

Figure 6.9. Nanosecond kinetic profiles of the transient absorption signals of Pt()TPTBP, excited at 430nm. Solid red lines depict the fits to the experimental data while blue lines represent the residual of the fit.

139 The bimolecular rate constant (kq) for quenching of the triplet in toluene by molecular oxygen was obtained by measuring the triplet state lifetime in solutions with different oxygen concentrations (Figure 6.9; upper right) and the plot of triplet lifetime vs. [O2] was linear with a slope that yielded a bimolecular rate constant for oxygen quenching of 2.26 x109 M-1 s-1 for Pt()TPTBP.

Oxygen quenching of the triplet state The energies of the triplet states can be extracted from the bimolecular rate constant of the quenching of the triplet state by molecular oxygen. An understanding of the transference of electronic energy to molecular oxygen from the triplet states of large molecules has become significant because of its impact in photodynamic therapy, as discussed in Chapter 1. Singlet molecular oxygen, O2(1g) is considered a leading candidate for the initiation of tissue damage in the presence of light, oxygen and an absorber.25 To detect singlet molecular oxygen, the S0 T1 energy gap should be below the energy gap of oxygen 1g 3 g transition ( 22. 5 kcal/mol/(1269 nm)) and a phosphorescence quantum efficiency is much higher than that of singlet oxygen.26 It has been demonstrated that exergonic energy transfer from triplet states to oxygen occurs with rate constants that are close to 2 x109 M-1 s-1. Rate constant values lower than that are found when the energy transfer from the triplet state to O2(1g) is endoergic.27 In the presence of oxygen the triplet states of both Zn()TPTBP and Pt()TPTBP decayed exponentially to a zero baseline. The first order rate constants of the decay were proportional to the O2 concentration. Bimolecular rate constants were found to be 1.20 x109 M1 -1

s (Table 3.4 in Chapter 3) for Zn()TPTBP and 2.26 x109 M-1s-1 for Pt()TPTBP (Table 6.5.).

The values of near 2 x109 s-1 are as anticipated for oxygen quenching of a triplet state having an

140 energy level higher than that of O2(1g) such that the reaction proceeds down the energy gradient.26 At room temperature, Zn()TPTBP clearly showed a luminescence signal due to singlet oxygen to the red of fluorescence (at 1270 nm) in aerated pyridine solution. The energy of the triplet of Zn() and Pt()TPTBP complexes were calculated according to the scheme and equation described in chapter 2 and gathered in Table 6.5.

M()TPTBP Zn Pt

10-9 kq/ M-1s-1 1.20 2.26

Keq 0.0109 0.205

ET/kcal.mol-1 21.16 22.90

ET/(eV/nm) 0.917/1352 0.993/1248

Table 6.6. Equilibrium derived triplet state energies for Pt and Zn complexes. Pt is in toluene solution and Zn in 1% pyridine-toluene solution.

The values in the table represent the adiabatic values corresponding to the energies of the triplet states after relaxation of the molecule to the minimum T1 potential energy surface and can be compared with Eadia values obtained by calculation.

Summary and Conclusions The excited state spectral and dynamic behavior of the Pt()TPTBP complex has been investigated by ultrafast transient spectrometry and interpreted with relativistic DFT and TDDFT calculations to see the heavy metal effect on the photophysics of metallotetrabenzoporphyrins.

141

S1

T1

0.5 ps

42 s
2

S0

Reaction coordinate Figure 6.10. Proposed excited state deactivation mechanism for Pt()TPTBP.

It was found that the optically produced S1 state is rapidly deactivated through the macrocycles T1 state localized on the system. The TDDFT calculations has shown that triplet ,* was the only state below S1. Heavy metal effects on the photophysics of third row transition metals can be attributed to the spin-orbit interaction that raises the energy of the unoccupied d orbital and enhance the intersystem crossing process. The lifetime of the triplet state was decreased in Pt complex compare to Zn. There is no metal-associated d,d or charge transfer excited state available in Pt()TPTBP complex. The higher energy gap between d,d/LMCT states and the singlet (,*) excited state obviated fast non-radiative deactivation as had been observed in the first row transition metal complexes.

142 The Pt complex showed a hypsochromic shift of the Q band and corresponding triplet (,*) state energy relative to the first row metallotetrabenzoporphyrins. Comparison of the Pt with first row transition metal gives an insight of the effect of 3d orbitals on the photophysics of tetrabenzoporphyrins.

References (1) (2) Mills, A.; Lepre, A. Anal. Chem. 1997, 69, 4653. Aartsma, T. J.; Gouterman, M.; Jochum, C.; Kwiram, A. L.; Pepich, B. V.;

Williams, L. D. J. Am. Chem. Soc. 1982, 104, 6278. (3) (4) Solovyov, K. N.; Borisevich, E. A. Physics-Upekshi 2005, 48, 231. Busetti, A.; Soncin, M.; Reddi, E.; Rodgers, M. A. J.; Kenney, M. E.; Jori, G. J.

Photochem. Photobiol. B: Biol. 1999, 53, 103. (5) Lai, S.-W.; Hou, Y.-J.; Che, C.-M.; Pang, H.-L.; Wong, K.-Y.; Chang, C. K.; Zhu,

N. Inorg. Chem. 2004, 43, 3724. (6) Kalyanasundaram, K. Photochemistry of Polypyridine and Porphirin Complexes;

Academic Press: London, 1992. (7) Mink, L. M.; Neitzel, M. L.; Bellomy, L. M.; Falvo, R. E.; Boggess, R. K.;

Trainum, B. T.; Yeaman, P. Polyhedron 1997, 16, 2809. (8) (9) Hanson, L. K.; Gouterman, M.; Hanson, J. C. J. Am. Chem. Soc. 1973, 95, 4822. Ponterini, G.; Serpone, N.; Bergkamp, M. A.; Netzel, T. L. J. Am. Chem. Soc.

1983, 105, 4639. (10) 4015. Kim, D.; Holten, D.; Gouterman, M.; Buchler, J. W. J. Am. Chem. Soc. 1984, 106,

143 (11) (12) (13) (14) Liao, M. S.; Scheiner, S. Chemical Physics 2002, 285, 195. Pyykko, E. Chem. Rev. 1988, 88, 563. Bond, G. C. J. Mol. Catalysis A: Chem 2000, 156, 1. Romaniello, P.; Aragoni, M. C.; Arca, M.; Cassano, T.; Denotti, C.; Devillanova,

F. A.; Isaia, F.; Lelj, F.; Lippolis, V.; Tommasi, R. J. Phys. Chem. A 2003, 107, 9679. (15) (16) Rosa, A.; Baerends, E. J. Inog.Chem 1994, 33, 584. Soldatova, A. In Department of Chemistry; Bowling Green State University:

Bowling Green, 2007; Vol. Ph.D. (17) (18) Rosa, A.; Baerends, E. J. Inog.Chem 1992, 31, 4717. Rosa, A.; Ricciardi, G.; Baerends, E. J.; van Gisbergen, S. J. A. J. Phys. Chem. A

2001, 105, 3311. (19) Rogers, J. E.; Nguyen, K. A.; D. C. Hufnagle; D. G. McLean; Su, W.; M.Gossett,

K.; Burke, A. R.; A.Vinogradov, S.; Pachter, R.; Fleitz, P. A. J. Phys. Chem. A 2003, 107, 11331. (20) 2004, 28, 676. (21) Rihter, B. D.; Kenney, M. E.; Ford, W. E.; Rodgers, M. A. J. J. Am. Chem. Soc. Brown, R. J. C.; Kucernak, A. R.; Long, N. J.; Mongay-Batalla, C. New J. Chem.

1993, 115, 8146. (22) Borek, C.; Hanson, K.; Djurovich, P. I.; Thompson, M. E.; Aznavour, K.; Bau, R.;

Sun, Y.; Forrest, S. R.; Brooks, J.; Michalski, L.; Brown, J. Angew. Chem. Int. Ed. 2007, 46, 1109. (23) Rozhkov, V. V.; Khajehpour, M.; Vinogradov, S. A. Inorg. Chem. Comm.

2003, 42, 4253.

144 (24) (25) Callis, J. B.; Knowles, J. M.; Gouterman, M. J. Phys. Chem. 1973, 77, 154. Firey, P. A.; Ford, W. E.; Sounik, J. R.; Kenney, M. E.; Rodgers, M. A. J. J. Am.

Chem. Soc. 1988, 110, 7626. (26) Pelliccioli, A. P.; Henbest, K.; Kwag, G.; Carvagno, T. R.; Kenney, M. E.;

Rodgers, M. A. J. J. Phys. Chem. A. 2001, 105, 1757. (27) Gunaratne, T.; Kennedy, V. O.; Kenney, M. E.; Rodgers, M. A. J. J. Phys. Chem.

A 2004, 108, 2576.

145 CHAPTER 7: SUMMARY AND CONCLUSIONS In this work, the investigation of the photophysical properties of the metallotetraphenyltetrabenzoporphyrins coordinated with first row transition metals with Cr(III), Mn(III), Co(II), Ni(II), Cu(II) and Zn(II) have been reported. Comparison has been made with Pt(II) and Pd(II) analogues to see the effect of the heavy metals to the deactivation kinetics. Transient absorption spectrometry with femtosecond and nanosecond time resolution has been employed along with DFT/TDDFT calculations to provide a detailed understanding of the sequence of events that follow Q band photo-excitation. The comparison has been done to address the effect of the nature of the central metal on the deactivation schemes for the excited states of metal-centered meso-tetraphenyltetrabenzoporphyrins. The first row transition metal complexes of tetraphenyltetrabenzoporphyrins have advantageous properties. Among them, a high molar absorption coefficient in the red spectral region and a fast radiationless decay of the excited states converting the photon energy into the thermal event make them useful in potential applications such as photothermal therapy which is a promising approach to tumor treatment. The ground and excited state properties of Zn()TPTBP have been investigated and the results were described in chapter 3. It showed the excitation to Q band produced vibrationally hot localized singlet (,*) and after cooling it decayed to the ground state through triplet state and fluorescence. TDDFT results indicated that below the singlet (,*), there are only ,* states can be seen and the lowest energy is responsible for the triplet state. For Co()TPTBP, the first observed transient which is a localized triplet state was converted to a hot d,d state, wherein intramolecular cooling occurred and completed within 3 ps. After cooling, the d,d state decayed into the ground state in an exponential manner having a 17 ps lifetime. The TDDFT calculations showed that there are two d,d states lying below the triplet state (1.57 eV) being a (d,dz2), 12E as the lowest, situated 0.81 eV vertically above

146 the ground state with the same multiplicity as the ground state. This state arises from the transition from the anti-bonding 39e molecular orbital with 60% on the d metal character to the empty dz2 spin orbital. So, the observed d,d state having a 17 ps lifetime was assigned to the 12E. Similar to Co()TPTBP, the first observed transient in Cu()TPTBP was assigned to the triplet state that equilibrate with an LMCT state; ground state repopulation occurred via a lower lying LMCT state. The dependence of the observed lifetime on solvent polarity confirmed the participation of the LMCT state in the TDDFT calculations overall deactivation process. The repopulation was completed within 500 ps. And also TDDFT calculations showed that below the triplet state there are two LMCT states that can be responsible for the observed lifetime shortening. After 640 nm excitation in Cr()TPTBPCl, the S1 state undergoes fast intersystem crossing (4S14T1), within a very short period of time (ca.0.05 ps lifetime) to 4T1 state. The
4 4

T1 state of Cr()TPTBPCl in toluene deactivated with a lifetime of 224 ps, resulting the T1 6T1 equilibrium. In benzonitrile solution 4T1 of Cr()TPTBPCl showed a lifetime of

90 ps. A substantial decrease in the lifetimes of photoexcited Cr()TPTBPCl in benzonitrile indicated the possible existence of a CT state that acts as a quenching state of the tripmultiplet state. 6T1 state should have a longer lifetime which was unable to find using the nanosecond transient absorption set up here. In Mn()TPTBPCl , the excited sing-quintet, 5S1(,*) state deactivated to the tripquintet, 5T1(,*) within the instrument response time. Within short time period afterwards, it generated a hot d,d state wherein cooling occurred within 4 ps. Subsequently the cooled d,d state repopulated the ground state with a 120 ps lifetime. With Pt analog, it was found that a localized S1 state undergoes fast intersystem crossing (ca.500 fs lifetime) to a triplet 3(,*) state. A low fluorescence quantum yield

147 (0.0003) was observed and it showed a high yield of phosphorescence. The triplet state lifetime was found to be ca. 41 s significantly shorter than Zn triplet state indicating that faster intersystem crossing due to spin orbit interaction introduced by the heavy Pt atom in the third row transition series. Vertical excitation energies computed for the lowest optically allowed and silent states showed that there is only the triplet state lie below the singlet state proving the above mentioned mechanism. In summary, with the aim of exploring the role of the central metal on the photophysics of MTPTBPs, transient absorption spectrometry with femtosecond and nanosecond time resolution has been employed. Experimental results have been interpreted with the help of DFT/TDDFT calculations with special emphasis on the nature and energies of the low lying excited states along the relaxation pathway of the photo-generated * state. The two approaches were brought together to generate a detailed understanding of the sequence of events that follow photo-excitation. The first row transition metal introduced low-lying electronic states that can serve as intermediates in the deactivation sequence by providing a series of low energy radiationless transition. A fast dissipation of the photon energy by the thermal radiationless event can be useful to implement those complexes as photothermal sensitizers.

APPENDIX A: ENERGIES AND PERCENTAGE COMPOSITION OF THE HIGHEST OCCUPIED AND LOWEST UNOCCUPIED MOLECULAR ORBITALS OF M()TPTBP, M= Zn, Co, Cu, Pt, Pd EXPRESSED INTERMS OF INDIVIDUAL ATOMS

Zn()TPTBP C 5(2pz) 2(2py) 44(2pz) 4(2py) 3(2px) 4(2pz) 35(2pz) 7(2px) 3(2py) 3(2pz) 4(2py) 4(2pz) 2(2px) 4(2pz) 6(2py) 8(2py) 2(2pz) C Cm Co C1 C2 C3 3(2Py) 2(2Pz) C4 8(2py) 5(2pz) -

MO

E,eV

Zn

17a2

-1.787

Cmeso Un occupied 14(2pz) 2(2py) 18(2pz) 3(2px) 2(2py) 10(2pz) 11(2pz) 2(2px) 2(2py) 7(2pz)

40e

-2.863

12(2pz)

18b1

-4.473

occupied 14(2pz) 3(2px) 2(2py) 10(2pz) 1(2px) 1(2py) 1(2pz)

4(2py) 2(2py) 4(2py) 1(2pz)

1(2py)

22b2

-4.843

2(3Pz)

39e 1(2py) 6(2pz) 3(2pz) 1(2py) 5(2px) 5(2py) 2(2s)

-5.673

18(2pz) 7(2px) 14(2pz) 23(2pz) 1(2py) 4(2px) -

45(2pz) 6(2py) 11(2pz) 1(2py)

52(2pz) 7(2py) 1(2px) 3(2pz) 1(2py) 7(2pz) 2(2pz) 1(2py) 5(2pz) 1(2py) 10(2pz) 2(2py) 1(2px) -

23b2

-5.687

17(3dxy)

3(2py) 2(2pz)

23a1

-5.851

38(2px) 13(2pz) 11(2s) 23(2pz) 28(2pz) 5(2px) 5(2py) 6(2pz) 1(2px)

16a2

-5.897

25(2pz) 4(2px) 4(2py) 10(2pz) 2(2px) 2(2py)

148

Co()TPTBP N 2(3px) 21(2pz) 5(2py) 4(2pz) 2(2pz) 2(2pz) 5(2pz) 1(2px) 4(2pz) 3(2py) 5(2py) 6(2py) 2(2pz) 10(2pz) 2(2py) 11(2pz) 1(2px) 1(2py) 2(2px) 2(3s) 2(2Py) C C Cm Co C1 C2 C3 C4 -

MO

E,eV

Co

23b2 17(2pz) 5(2px) occupied 40(2pz) 10(2py) 10(2pz) 4(2py) 5(2pz) 2(2pz) 2(2py) 4(2pz) 2(2py) 3(2px) 5(2pz) 1(2py) 47(2pz) 11(2py) 1(2px) 7(2pz) 2(2px) 4(2pz) 3(2pz) 1(2py) 3(2pz) 2(2pz) 23(2pz) 5(2px) 3(2py) 5(2pz)

-2.412

60(3dx2-y2)

Cmeso un occupied -

40e

-2.751

5(3d)

20(2px) 8(3s) 3(2pz) 12(2pz) 2(2py) -

18b1

-4.411

2(2py) 2(2pz) 3(2py) 2(2px)

39e

-4.938

60(3d)

7(2pz)

22b2

-4.959

2(2pz)

22(2pz) 2(2px)

23a1

-5.126

4(2pz) 1(3d) 1(2py) 1(2px)

17b1

-5.476

82(3dz2) 8(4s) 92(dxy)

38e -

-5.778

3(3d)

3(2pz) 1(2px) 1(2px) 1(dx2-y2) 1(2pz)

16a2

-5.893

27(1pz) 6(2px) 2(2py) 33(2pz) 8(2px)

9(2pz) 2(2py) 1(2px) 9(2pz) 6(2py) 2(2px)

149

Cu()TPTBP C 5(2pz) 3(2py) 23(2pz) 5(2py) 2(2px) 2(3px) 2(3s) 3(2pz) 4(2pz) 3(2pz) 2(2py) 32(2pz) 8(2px) 4(2py) 4(2pz) 3(2py) 4(2py) 1(2pz) 4(2py) 2(2pz) 2(2py) 2(2pz) 2(2py) 3(2py) 2(2pz) 1(2py) 2(2py) 3(2pz) 2(2px) 5(2pz) 5(2py) 7(2py) 3(2pz) 3(2Py) 2(2Pz) C Cm Co C1 C2 C3 C4 7(2py) 7(2pz) -

MO

E,eV

Cu

17a2 19(2Pz) 3(2Px) occupied 6(2pz)

-1.823

Cmeso Un occupied 13(2pz) 3(2py) 16(2pz) 3(2px) 3(2py) 10(2pz) 2(2py) 1(2px) 10(2pz) 3(2px) 2(2py) 6(2pz) 1(2py) 1(2pz)

40e

-2.835

11(2pz) 2(2py)

23b2

-4.058

29(2px)

8(3s)

18b1

-4.452

41 (3dx2-y2) 4 (4dx2-y2) 13(2pz) 3(2px) 2(2py) 9(2pz) 2(2px) 1(2py) -

22b2

-4.916

39e 5(2pz) 5(2pz) 2(2pz) 2(2py) 2(2pz) 1(2py)

-5.570

3(3dx2-y2) 1(3Pz) 10(3d)

26(2pz) 1(3s) 20(2pz)

40(2pz) 7(2py) 6(2pz) 1(2px)

49(2pz) 9(2py) 2(2px) 4(2pz) 1(3d) 7(2pz) 1(2px)

38e

-5.840

5(3d)

4(2pz)

23a1

-5.843

2(3dz2)

24(2pz)

12(2pz) 2(2py) 2(2px) 6(2pz) 3(2px) 1(2py) -

16a2

-5.890

8(2pz) 2(2py) 1(2px) 16(2pz) 3(2py) 2(2px) 24(2pz) 6(2py) 6(2px) 5(2pz) 1(2px)

11(2pz) 2(2py) 3(2px) 23(2pz) 4(2py) 2(2px) 22(2pz) 4(2px) 4(2py) 9(2pz) 2(2px) 2(2py)

150

Pt()TPTBP C 5(2pz) 2(2py) 23(2pz) 3(2py) 4(2pz) 4(2pz) 12(2pz) 2(2py) 4(2pz) 4(2pz) 2(2py) 2(2pz) 3(2pz) 3(2py) 25(2pz) 4(2px) 3(2py) 4(2py) 3(2py) 3(2py) 1(2pz) 3(2pz) 2(2px) 2(2py) 1(2pz) 1(2pz) 5(2pz) 7(2py) 8(2py) 2(2pz) 3(2Py) 2(2Pz) C Cm Co C1 C2 C3 C4 9(2py) 5(2pz) 1(2py)

MO

E,eV

Pt

24a2

-1.779

Cmeso un occupied 14(2pz) 2(2py) 17(2pz) 3(2px) 2(2py) 11(2pz) 1(2py) 11(2pz) 2(2px) 2(2py) 8(2pz) 1(2py)

63e

-2.783

5(dyz)

12(2pz) 2(2py)

29b1

-4.480

19(2pz) 3(2px) occupied 15(2pz) 3(2px) 2(2py) 10(2pz) 1(2px) 1(2py) 2(2pz)

35b2

-5.060

1(2Pz)

20(2pz)

62e 9(2pz) 1(2py) 5(2pz) 2(2pz) 1(2py) 3(2pz) 1(2py) 2(2px)

-5.189

33(5dxz)

14(2pz)

44(2pz) 7(2py) 12(2pz) 1(2py) 2(2px) -

50(2pz) 7(2py) 2(2px) 4(2pz) 1(dxz) 8(2pz) 1(2px)

40a1

-5.654

63(5dz2) 15(s)

7(2pz)

61e

-5.793

1(5dxz)

23a2

-5.887

3(2pz) 2(2py) 1(2px) 8(2pz) 1(2px) 2(2py) 6(2pz) 1(2px)

13(2pz) 5(2px) 3(2py) -

39a1

-6.044

13(5dz2) 3 (6s)

14(2pz) 2(2px)

26(2pz) 1(2px) 2(2py) 47(2pz) 9(2px) 5(2py) 23(2pz) 4(2py) 4(2px)

151

Pd()TPTBP C 1(2pz) 2(2px) 24(2pz) 3(2py) 3(2pz) 3(2pz) 4(2pz) 12(2pz) 2(2py) 4(2pz) 2(2px) 2(2pz) 3(2pz) 3(2py) 26(2pz) 3(2px) 3(2py) 2(2px) 2(2py) 4(2py) 1(2pz) 10(2pz) 1(2py) 11(2pz) 2(2px) 2(2py) 2(3s) C Cm Co C1 C2 C3 C4 1(2py) 2(2px) 2(2pz) 3(2py) -

MO

E,eV

Pd

33b2

-2.278

Cmeso un occupied 2(2pz) 1(2py)

59e

-2.801

43(3dxy) 3(4dxy) 1(5dxy) 3(dyz) 20(2pz) 3(2px) occupied 15(2pz) 10(2px) 1(2py) -

28(2px) 10(3s) 2(2pz) 12(2pz) 2(2py)

28b1

-4.483

32b2

-5.017

23(2pz)

58e 3(2px) 5(2pz) 2(2pz) 1(2py) 2(2pz) 1(2px) 1(2px)

-5.349

26(5dxz)

17(2pz)

43(2pz) 6(2py) 2(1pz) 13(2pz) 3(2py) 1(2px) -

50(2pz) 7(2py) 2(2px) 4(2pz) 1(dxz) 6(1pz) 1(2px)

37a1

-5.672

61(5dz2) 10(s)

9(2pz)

57e

-5.802

2(4dyz)

9(2pz)

22a2

-5.888

10(2pz) 2(2px) 1(2py) 6(2pz) 1(2px)

36a1

-5.981

14(4dz2) 3 (5s)

14(2pz) 3(2px)

3(2pz) 2(2py) 2(2px) 26(2pz) 3(2px) 5(2py) 36(2pz) 7(2px) 4(2py) -

13(2pz) 2(2px) 2(2py) 10(2pz) 2(2px) 2(2py) 22(2pz) 4(2py) 4(2px)

152