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Theoretical and Computational Aspects of Magnetic Molecules

Thesis

Submitted in partial fulfillment of the requirements for the degree of

Doctor of Philosophy

Submitted by

Md. Ehesan Ali

(02403001)

Under the Guidance of Prof. S. N. Datta

Ali ( 02403001 ) Under the Guidance of Prof. S. N. Datta Department of Chemistry Indian

Department of Chemistry Indian Institute of Technology, Bombay

January, 2007

Dedicated to My Parents

Approval Sheet

Thesis entitled “Theoretical and Computational Aspects of Magnetic

Molecules by Md. Ehesan Ali is approved for the degree of Doctor of

Philosophy

Date:

Place: IIT–Bombay

Examiners

Supervisor

Chairman

Certificate of course work

This is to certify that Mr. Md. Ehesan Ali was admitted to the Ph.D. program on July 2002. He successfully completed all the courses required for Ph.D. program. The details of the course work are given below.

Sr. No.

Course No.

Course name

Credit

 

1 CH 521

Interpretative Molecular Spectroscopy

6.00

 

2 CH 559

Solid State Chemistry and its Applications

6.00

 

3 CH 821

Topics in Chemistry I

6.00

 

4 CH 842

Elements of Advanced Molecular Quantum Mechanics

6.00

 

5 CH 831

Advanced Laboratory Techniques

8.00

 

6 CHS 802

Seminar

4.00

 

Total credit

36.00

Place: IIT–Bombay

Deputy Registrar (Academic)

Contents

Chapter 1:

Magnetic Molecules

1.1. Introduction

1

1.2. Ferromagnetic Molecules

1

1.3. Insights from Literature Survey

2

1.4. Diradicals

3

1.4.1.

Stable Diradicals

6

1.4.2.

Triradicals and Polyradicals

7

1.5. Interesting Phenomenon related to Magnetic Molecules

8

1.5.1. Single Molecule Magnets

8

1.5.2. Photomagnetism

9

1.5.3. Spintronics

10

1.6. Scope of Molecular Magnetism

10

1.7. Objectives and Organization of the Thesis

11

1.8. References

12

Chapter 2:

Theoretical Background

2.1. Introduction

17

2.2. Theoretical Background

19

2.2.1 Single Determinant Approach

19

2.2.2 Two-Determinant Configuration

21

2.2.3 Orbital Perturbation Theory

22

2.2.4 SCF energy

24

2.3. Spin Hamiltonian Treatment

26

2.3.1

Base line

27

2.3.2.

Spin Hamiltonian

27

2.3.3.

Expectation Values

29

2.4. Coupling Constants

30

2.5. Discussion

33

2.5.1. Factors Influencing Accuracy

33

2.5.2. Numerical Tests

33

2.6. Conclusions

36

2.7. References

37

Chapter 3:

Organic Fused–Ring Diradicals

3.1. Introduction

40

3.2. Methodology

42

3.3. Energy Differences

43

3.3.1.

4-oxy-2-naphthalenyl methyl

44

3.3.2.

1,8-naphthalenediylbis(methyl)

45

 

3.3.3. 1-imino-1-naphthalenyl methyl

45

3.3.4. 1,8-naphthalenediylbis(amidogen)

46

3.3.5. 8-methyl-1-naphtyl carbine

47

3.3.6. 8-methyl-1-naphthalenyl imidogen

48

3.3.7. 8-methyl-1-naphthyl diazomethane

49

3.4. Conclusions

50

3.5. Reference

52

Chapter 4:

Bis–Nitronyl Nitroxide Diradicals: Influence of Length and Aromaticity of Couplers

4.1. Introduction

54

4.2. Theoretical Background

54

4.3. Computational Strategy

54

4.4. Results and Discussion

55

4.4.1. Rationalization

61

4.4.2. SOMO-SOMO Energy Level Splitting

63

4.4.3. Isotropic Hyperfine Coupling Constant

65

4.5. Diphenylene Acetylene Coupler

65

4.6. Conclusions

70

4.7. Reference

72

Chapter 5:

Influence of Aromaticity in Intramolecular Magnetic Coupling

5.1. Introduction

74

5.2. Computational Methodology

74

5.3. Results and Discussion

76

5.3.1. Bond Order and Dihedral Angles

77

5.3.2. Nuclear Independent Chemical Shift

78

5.3.3. SOMO-SOMO Energy Splitting

81

5.3.4. Isotropic Hyperfine Coupling Constant

81

5.4. The m-Phenylene Couplers

82

5.4.1.

Calculations

83

5.5. Conclusions

89

5.6. Reference

91

Chapter 6:

Photomagnetism

6.1. Introduction

92

6.2. Technical Details and Results

93

6.3. Conclusion

98

6.4. References

98

Chapter 7:

Dinuclear Copper Complex

 

7.1. Introduction

99

7.2. Computational Methodology

102

7.3. Choice of Magnetic Orbitals

102

7.4. Results and Discussion

104

7.5. Conclusions

110

7.6. References

110

Conclusions

112

Summary

i

Acknowledgment

Chapter 1

Magnetic Molecules

This chapter describes a general introduction to magnetic molecules. A detailed literature survey is also presented. The scope of molecular magnetism and the objectives of the Thesis are discussed.

Chapter 1

Magnetic Molecules

1.1. Introduction

Magnetism has played a vital role in human civilization. The study of ferromagnetism has been traditionally concerned exclusively with the study of transition elements (like Fe, Co and Ni), alloys and metal oxides. This field of study has provided numerous technological rewards based on the exploitation of such materials. In recent years, the focus of research on magnetism has turned towards molecular systems and crystals. The reasons for this trend are tunability of magnetic properties as a result of alterable chemical structures, bio-activity of organic molecules, photo-control of chemical structure, and structure-property relationships. In other words, the molecule can be tailored to exhibit desired magnetic properties. Invariably, the building block of such magnetic materials are open-shell molecules such as organic monoradicals, diradicals in which nonbonding molecular orbitals contain unpaired electrons, and transition metal complexes with unpaired d-electrons. A large number of high-spin magnetic molecules have been recently synthesized and investigated. 1

1.2. Ferromagnetic Molecules

Molecular ferromagnetism results when the electronic spins in a single molecule are coupled in a parallel orientation. In organic diradicals, two unpaired electrons at two different non-bonded molecular orbitals (NBMOs) are coupled through the spacer in either parallel (S=1) or anti-parallel (S=0) fashion, resulting in ferromagnetic or antiferromagnetic interaction respectively. There are several rules to qualitatively predict the ground spin state of such diradicals as discussed below. According to Longuest-Higgins 2 , the number of NBMOs can be calculated as n = (N

2T) where N is the total number of the carbon atoms and T is the maximum number of possible double bonds. This simple rule predicts the ground spin state of para- benzoquinodimethan (1) (Figure 1.1). Four double bonds are possible and the number of NBMOs is zero. Hence an antiferromagnetic interaction is observed. For meta- benzoquinodimethan (2) (Figure 1.1), there are two NBMOs and according to the Hund’s rule, a triplet (S=1) ground state is expected. 3 From valence-bond formalism, Ovchinnikov 4 suggested that the ground state spin S

can be determined as S = (n* n)/2 for n* > n, where n* and n are the numbers of starred and unstarred alternate carbon atoms. This rule predicts the meta- and para- benzoquinodimethan to be in triplet and singlet ground spin states respectively (Figure 1.2).

Chapter 1

Magnetic Molecules

1 2 S = 0 S = 1
1
2
S = 0
S = 1

Figure 1.1. para- and meta- isomers of benzoquinodimethan.

Figure 1.2.

* * * * * * * * 2 1 S = 1 S =
*
*
*
*
*
*
*
*
2
1
S = 1
S = 0

*

Figure 1.2. * * * * * * * * 2 1 S = 1 S

Predictions of ground state spin in starred/unstarred model and in the spin polarization model.

The starred/unstarred model is very closely related to the concept of spin polarization that can also predict the nature of the magnetic exchange interaction. 5 Large positive spin densities on atoms in conjugated systems induce small negative spin densities on neighboring atoms. This spin polarization can be rationalized by considering the formation of the chemical bond. The quantum chemical exchange favors a parallel orientation of the spins of the electrons in σ- and π-orbital on the same atom over an antiparallel orientation. Spin alternation rule that has been explained and demonestrated in UHF treatment can also predict the ferro- and anti-ferromagnetic exchange interaction. 6

1.3. Insights from Literature Survey The first molecular ferromagnet, Fe(Cl)[S 2 CN(C 2 H 5 ) 2 ] 2 , was reported in 1972 and its crystal was found to have ferromagnetic ordering at 2.43 K. 7 Subsequently, Miller et al synthesized a charge-transfer salt, composed a ferrocene derivative and tetracyanoethylene with a Curie temperature of T C of 4.8 K. 7 The first pure organic magnet, β crystalline phase of p-nitrophenyl nitronylnitroxide (3) that orders magnetically at 0.65 K, 8 is one of the major successes in modern research. In 1991, Wudl and coworkers discovered the organic molecular ferromagnet, tetrakis(dimethylamino)ethylenefullerene[60] (TDAE-C 60 , 4) with Curie temperature of 16.1

Chapter 1

Magnetic Molecules

K. 9 The origin of the ferromagnetism in TDAE-C 60 has been the subject of various studies. Its synthesis initially raised the hope that the higher T C values would soon be observed by using other donors. But TDAE-C 60 remained as the organic material with the highest T C until 1998 when Mihailovic reported 3-aminophenyl-methano-fullerene[60]-cobaltocene with a slightly higher T C of 19 K. 10 Rassat et al. have synthesized 1,3,5,7-tetramethyl-2-6- diazaadamantane N, N'-dioxyl (5) (T C = 1.48 K). 11 In 5, the two electron spins align in the parallel fashion through intramolecular interaction, while the intermolecular interaction is also ferromagnetic in nature. This phenomenon results a three-dimensional ferromagnetic order below the Curie temperature.

O N O N N O O
O
N
O
N
N
O
O

3

O N N Me NMe 2 N 2 O Me NMe 2 N 2 4
O
N
N
Me
NMe
2 N
2
O
Me
NMe
2 N
2
4
5

Figure 1.3. Organic ferromagnetic molecules.

1.4. Diradicals All the above examples of ferromagnetism arise from the intermolecular ferromagnetic interactions. The intramolecular ferromagnetic order occurs in organic diradicals and in dinuclear transition metal complexes. The simplest example of intramolecular ferromagnetic interaction is trimethylenemethane (TMM, 6). TMM is a diradical that has been widely investigated in different areas of chemistry. It was isolated in matrix by Dowd in 1966. The significant and diverse impact of TMM has resulted from the synthesis and studies of TMM derivatives that are stable and can be tailored to desired molecular properties. TMM is the triplet ground state diradical with a very large singlet- triplet energy gap (ΔE ). The estimated energy gap by photoelectron spectroscopy is in the

ST

12

range of 1316 Kcal mol . This range is confirmed by different computational studies.

The large ΔE indicates a very strong ferromagnetic interaction between the two radical centers. As a result, TMM is a very attractive building block in molecular magnetism.

1 13

14

ST

Chapter 1

Magnetic Molecules

Ar C Ar . . TMM Ar Ar 6 7 t-Bu t-Bu t-Bu O N
Ar
C
Ar
.
.
TMM
Ar
Ar
6
7
t-Bu
t-Bu
t-Bu
O
N
O
O
t-Bu
t-Bu
t-Bu
t-Bu
+
N
O
t-Bu
O
9
8

Ar

ArN O O t-Bu t-Bu t-Bu t-Bu + N O t-Bu O 9 8 Ar t-Bu

t-BuO O t-Bu t-Bu t-Bu t-Bu + N O t-Bu O 9 8 Ar Ar Figures

Figures 1.4. TMM and its analogous diradicals.

Rajca et al. synthesized a new stable diradical 7, which is a 3-fold symmetric analogue of TMM with no hetero atom substitution. This is similar but superior to 8 (Young’s diradical) and 9. All these diradicals are stable and have triplet ground states. But only 7 can be extended to form polyradicals with a strong ferromagnetic coupling whereas the other two are restricted due to their geometrical features. Recently, Shultz and coworkers have synthesized stable diradicals 10-13 and studied their magnetic properties. These radicals are TMM analogues. The authors noticed the structure-magnetic property relationship, that is, the correlation of the exchange parameters with the phenyl-ring torsion angles (φ). The strong ferromagnetic interaction can also be achieved via a benzene moiety (2). The ground state of ortho- and para- substituted diradicals are singlet. Spectroscopic studies of m-benzoquinodimethane (2) by Berson and their coworkers, Migirdicyan and Platz suggest a triplet ground state 18 and ab initio calculations predict a 10 Kcal mol 1 singlet-triplet energy gap. 19

16

14

17

15

Chapter 1

Magnetic Molecules

O O O O N N N N t-Bu t-Bu t-Bu t-Bu t-Bu t-Bu 10
O
O
O
O
N
N
N
N
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
10
11
O
O
N
N
O
t-Bu
t-Bu
N
t-Bu
t-Bu
13
12

Figure 1.5. Recently synthesized TMM analog diradicals.

The exchange coupling constant (J) is consistent with ferromagnetic (J F ) as well as antiferromagnetic (J A ) counterparts, that is, J = J F + J A. Antiferromagnetic coupling is generally found to be more effective than the ferromagnetic interaction. 20 Borden and Davidson observed that the presence of non-disjoint MO (different orthogonal NBMO arising from the common atom contributions) leads to a greater ferromagnetic coupling. 21

l eads to a greater ferromagnetic coupling. 2 1 14 15 1 6 Figure 1.6. Diradicals

14

l eads to a greater ferromagnetic coupling. 2 1 14 15 1 6 Figure 1.6. Diradicals

15

l eads to a greater ferromagnetic coupling. 2 1 14 15 1 6 Figure 1.6. Diradicals

16

Figure 1.6. Diradicals with two parallel couplers.

Chapter 1

Magnetic Molecules

The spectroscopic study of dimethylenecyclobutadiene (14), which is an example of ferromagnetic coupling via two parallel coupling units, suggests a triplet ground state. The ab initio calculations predict ΔE = 17.7 kcal mol . The spectroscopic studies of the matrix-

ST

1 22

1 23

isolated species 15 established its singlet ground state with ΔE > 1 kcal mol . Ab initio

ST

1 24

calculations suggest an energy gap of 5 kcal mol . For diradical 16, spin alternation rule predicts the singlet ground state.

25

1.4.1.

Stable Diradicals The first stable diradical (17) was synthesized by Schlenk almost a century ago, in

1915.

26 It was identified as a ground state triplet by EPR measurement in matrix. 27

A lot of

efforts has been applied to increase the stability and the magnetic exchange interaction in this species. 28 In fact, all the compounds 18-22 in Figure 1.7 show intense ESR spectra. 29 The heteroatoms as spin sites can be attached to a strong ferromagnetic coupler. For

example, 1013 are stable and ferromagnetically coupled diradicals. Stable, yet weakly

coupled diradicals are known. 2930 The stable diradicals with nitronyl nitroxide fragments are fascinating species in modern research on molecular magnetism. A large portion of this thesis will describe the computational studies on different Nitronyl Nitroxide systems. Till now a large number of nitronyl nitroxide (NN) based diradicals has been experimentally investigated. 31 The intramolecular magnetic exchange coupling constant, as well as the intermolecular interaction that depends upon the structure and the nature of a molecular crystal, control the magnetic properties of a molecule-based magnetic material. An estimate of the intramolecular exchange coupling constant is necessary prior to synthesizing a successful magnetic material based on organic diradicals or transition metal complexes. The recent development of computational techniques and theoretical methodologies has enabled the prediction of magnetic properties of the precursors. 32 Here we report the results of the study of a series of nitronyl nitroxide based diradicals with different conjugated magnetic couplers. The magnetic couplings are generally found to arise from spin polarization and spin

delocalization. 33 Lahti et al. 5 investigated a large number of π-conjugated couplers. They

noticed that most of the spin density is localized on the two-singly occupied σ orbitals

Chapter 1

Magnetic Molecules

(SOMOs) centered on the radical atoms. The large spin population polarizes the π electrons

near the radical centre. The total π spin density sums to zero over all sites in the singlet state,

but the individual sites may be polarized to have positive or negative spin densities. The spin polarization effect plays a major role in controlling the nature of the coupling. The presence of non-bonding molecular orbitals (NBMOs) in organic diradicals makes it difficult to properly evaluate the energy difference between the lowest states of different spin. The expected ground state spin may be predicted either by molecular orbital (MO) calculation or by a valence bond (VB) treatment. In the simple MO model, Hund’s multiplicity rules are often applied to molecules having degenerate or nondegenerate NBMOs, with the prediction of a triplet ground state. However, in a variety of conjugated systems the Hund’s criterion does not necessarily follow, and a singlet ground state results. TME and its derivatives are the simplest examples of such system. The low-spin nature of TME and the related disjoint systems was explained by a VB-type electronic exchange. A number of derivations were made to model the intramolecular exchange in connectivity-conjugated systems by Ovchinikov, 4 Klein, 34 Borden and Davidson 35 and Sinanŏglu. 36 In all these cases the simplistic MO theory and the Hund’s rule do not follow in a proper way. A large number of

computational studies have been performed on this issue. 3739 It is observed that the spin

polarization argument is more useful to understand the spin density distribution in an open shell system.

and the spin density distribution in an open shell system. 1 7 t -Bu R R

17

t-Bu

R R X t-Bu t-Bu R=H, X=H 18 R=Me, X=H 19 R=i-Pr, X=H 20 R=Me,
R R
X
t-Bu
t-Bu
R=H, X=H
18
R=Me, X=H
19
R=i-Pr, X=H
20
R=Me, X=Me 21
R=CF3, X=H
22

t-Bu

Figure 1.7. The stable Schlenk diradicals (17) and its derivatives.

1.4.2. Triradicals and Polyradicals Triradicals are relatively unusual. The nature of magnetic interaction between the

radical centers can be divided into three categories: (1) Two 1,3 connected benzene rings in a

Chapter 1

Magnetic Molecules

‘linear’ arrangement, (2) 1,3,5 substituted benzene ring, and (3) three 1,3,5 connected benzene rings in a “closed loop” arrangement as shown in Figure 1.8. The expression for the magnetic exchange coupling constant is J = ΔE QD , and 3J = ΔE QD , and 3J = ΔE QD for the three categories respectively.

J = Δ E Q D for the three categories respectively. Δ E Q D =

Δ E QD =J

the three categories respectively. Δ E Q D = J Δ E Q D =3J Figure

Δ E QD =3J

Figure 1.8. Triradicals of three types.

Δ E Q D =3J Figure 1.8. Triradicals of three types. Δ E QD =3J Polyradicals

Δ E QD =3J

Polyradicals (23) are most promising very-high-spin molecular systems. Rajca and co-workers have synthesized decaradicals, which posses S = 5 high-spin state. 40 Due to the presence of spin defects in single ferromagnetic pathway, the experimental magnetization is always less than the predicted value. To overcome this problem, Rajca introduced calix(4)arene in the centre while triarylmethyl radicals are linked to it, and this provides multiple pathways for the ferromagnetic interaction (24). 41

1.5. Interesting Phenomena Related to Magnetic molecules

Several interesting areas of research have been emerged from molecular magnetism. Currently a large number of physicists and chemists are involved in these exciting areas. A few of these are described below.

1.5.1. Single Molecule Magnet (SMM) The single molecule magnet is an assembly of individual magnetic molecules. To be a single-molecule magnet, the object must show a net magnetic spin and have no magnetic interaction between molecules. Caneschi et al. reported the first magnetic molecules [Mn 12 O 12 -(O 2 CMe) 16 (H 2 O) 4 ] with a ground-state spin of S =10 in 1991. 42 The SMM term was first used by Hendrickson in 1996. 43 The Mn 12 O 12 complex and its analogous complexes shows SMM behaviors but in the low temperature range with very small the spin barrier (50

Chapter 1

Magnetic Molecules

cm 1 ). To increase the critical temperature of SMM, (above which it behaves as

n n n n n n
n
n
n
n n
n

23

Ar Ar Ar Ar Ar Ar Ar Ar Ar Ar Ar Ar Ar Ar Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar

24

Figure 1.9. Magnetic plastics S=10 for 23 and S5000 for 24.

Ferromagnetic, antiferromagnetic or paramagnetic) the total spin quantum number S should

be very high and there must be a highly negative zero-field splitting parameters.

A number of theoreticians and experimentalists are making efforts to increase the critical temperature of SMM to use them in molecular devices. 44 Recently Soler et al. have synthesized Mn 12 O 12 based SMM. 45 Davidson et al. calculated the magnetic properties of these substances using local spin model. 46

1.5.2. Photomagnetism

The extension of molecular photochromism results in the possibility of photo switching of magnetic properties. Matsuda et al. have synthesized a large number of photomagnetic molecules. 47 The number of coordination compounds is limited to some dithienylethylene derivatives, 48 tetracyanoethylene organomettalic compounds, spin crossover and valence-tautomeric complexes. From these perspectives, the Prussian blue analogue complexes are the most promising. Recently Dei have synthesized a very interesting

Chapter 1

Magnetic Molecules

photomagnetic [{Cu(tren)-NC} 6 Mo(CN) 2 ] 8+ complex. 49 A larger number of theoretical and experimental work has been performed on this issue. 50 1.5.3. Spintronics Spintronics is the "spin-based electronics" and also known as magnetoelectronics. This refers to the control of electric current through a manipulation of the spin of the electrons. It has been extensively investigated using layers of ferromagnetic materials from both fundamental and device application points of view, as in magnetic tunneling junctions (MTJ). 51-53

1.6. Scope of Molecular Magnetism

The materials which display cooperative magnetic phenomena yet are based on molecular building blocks have added advantages over conventional magnets such as low density, transparency, electrical insulation, low temperature fabrication as well as offering the possibility of combining magnetic behavior (either cooperative, or isolated, as in “spin- crossover compounds”) with other properties such as photo- or thermal responsiveness. In addition, there are often useful processing advantages such as the ability to deposit the materials as films, to functionalise them for attachment to substrates and possible biocompatibility.

Magnetic properties of these materials can have important practical applications for use in domestic appliances as well as in high-tech sciences. For example, in the rapidly evolving world of micro-electronics, electronic circuits and storage devices are decreasing in size and will eventually reach molecular dimensions. Thus, in future conventional semi- conductor technology could be abandoned in favour of new materials with molecular magnetic properties (“spintronics”) to build a computer. In addition to their small size, magnetic materials consisting of molecular entities have the advantage that the molecular precursors can be prepared under mild conditions in a directed synthesis and are therefore easily integrated into materials with well-defined magnetic, magneto-optic or magneto- electric properties. Spintronic devices are used in the field of mass-storage. Recently (in 2002) IBM scientists announced that they could compress massive amounts of data into a small area, at approximately one trillion bits per square inch (1.5 Gbit/mm²) or roughly 1 TB

Chapter 1

Magnetic Molecules

on a single sided 3.5" diameter disc. Although some applications have already arisen from this newly emerging field, it is still at an early stage of development. The ultimate rewards of producing devices based on magnetic systems are increased processing power and information storage, but this lie some way in the future. At present, the major requirements for the further successful development of this highly promising field of materials science are the production and investigation of a range of new systems and developing the basic research into the underlying principles, namely a detailed description of molecular magnetism.

Molecular magnetism is a field of research where the investigation of the magnetic properties of isolated molecules as well as of assemblies of molecules is undertaken. These molecules may contain one or more magnetic centers. The assemblies of molecules occurring in the solid state may be characterized by very weak interactions between the molecular entities, thereby displaying magnetic behavior very similar to that of the isolated molecules. They may consist of extended systems, in which strong magnetic interactions between the molecular entities are responsible for bulk magnetic properties.

1.7. Objectives and Organization of the Thesis

The main aim of my PhD work has been to investigate the phenomenon called molecular magnetism. A quantitative measure of magnetism in molecules is available in the form of the intramolecular magnetic exchange coupling constant J. A knowledge of J helps in predicting the magnetic moment and EPR frequency. Therefore, the objectives of this thesis turn out as

1. To theoretically investigate J for diradicals and compare the derived formula with those obtained by others;

2. To computationally investigate J for organic diradicals by using different ab initio methodology;

3. To explore the possibility of photo-activation of magnetic properties;

4. To briefly investigate the characteristics of a transition metal complex diraical, and understand the differences from organic diradicals.

The arrangement is

The present thesis has been arranged according to the stated objectives. as follows.

Chapter 1

Magnetic Molecules

A theoretical formalism for diradicals with nondegenerate HOMOs is given in

Chapter 2, where we present an N-electron interpretation of the spin Hamiltonian and subsequently show that the Yamaguchi and GND formula arise from special types of approximations.

In Chapter 3, fused-ring organic diradicals are investigated so as to determine the

ground spin states. The singlet-triplet energy gaps are calculated by using HF, post-HF and DFT methodologies. A good correlation between the experimental and calculated results is observed when the ST energy difference is large. However, these molecules are less important from the molecular magnetism point of view as these are very unstable. The broken symmetry (BS) method of calculations has been adopted for the work described in Chapter 47. Chapter 4 deals with a series of nitronyl nitroxide diradicals with different linear and cyclic couplers. Effects of structural features, like chain length, dihedral angles, etc., on J are investigated. We also predict the nature of magnetic exchange interaction in a few new molecules. The effect of aromaticity of benzene and polyacene couplers on the intramolecular J is discussed in Chapter 5. The investigation of the ground state magnetic properties of a few photochromic molecules is described in Chapter 6. Some of these photochromic molecules can act as photomagnetic switches. The investigation of magnetic properties of a dinuclear copper complex is discussed in Chapter 7. Summary of the thesis and the conclusions are given subsequently.

1.8. References

1. (a) Gatteschi, D.; Khan, O.; Miller, J. S.; Palacio, F. (Eds.), Magnetic Molecular Materials, Kluwer Academic Publishers, Dordrecht, 1991. (b) Kahn, O. (Ed.), Magnetism: A Supramolecular Function, Kluwer Academic Publishers, Dordrecht, 1996. (c) Lahti, P. M. (Ed.) Magnetic Properties of Organic Materials, Marcel Dekker, Inc., New York, 1999. (d) Miller, J. S.; Epstein.A. J. Angew. Chem., Int. Ed. Engl. 1994, 33, 385. (e) Rajca, A. Chem. Rev. 1994, 94, 871. (f) Miller,J. S.; Drillon, M. (Eds.) Magnetism: Molecules to Materials, Models and Experiments, Wiley-VCH, Weinheim, 2001. (g) Miller, J. S.; Drillon, M. (Eds.) Magnetism: Molecules to Materials II,Molecule-Based Materials, Wiley-VCH, Weinheim, 2001. (h) Miller, J. S.; Drillon, M. (Eds.) Magnetism: Molecules to Materials III, Nanosized Magnetic Materials, Wiley-VCH, Weinheim, 2001. (i) Miller, J. S.; Drillon, M. (Eds.)

Chapter 1

Magnetic Molecules

Magnetism: Molecules to Materials IV, Molecule-based Materials (2), Wiley-VCH, Weinheim, 2002. (j) van Meurs, P.J. High-Spin Molecules of p-Phenylenediamine Radical Cations, PhD Thesis, Technische Universiteit Eindhoven, 2002. (k)

2. Longuet-Higgins, H. C. J. Chem. Phys. 1950, 18, 265.

3. Woodgate, G.K.; Elementary Atomic Structure, physics, McGraw-Hill, 1970.

4. Ovchinnikov, A. A. Theoret. Chim. Acta. 1978, 47, 297.

5. (a) Lahti, P. M.; Ichimura, A. S. J. Org. Chem. 1991, 56, 3030. (b) Ling, C.; Minato, M.; Lahti, P. M.; van Willigen, H. J. Am. Chem. Soc.1992, 114, 9959. (c) Minato, M.; Lahti, P. M. J. Am. Chem. Soc. 1997, 119, 2187.

6. (a) Trindle, C.; Datta, S. N. Int. J. Quantum Chem. 1996, 57, 781. (b)Trindle, C.; Datta, S. N.; Mallik,

B. J. Am. Chem. Soc. 1997, 119, 12947.

7. (a) Wickman, H. H. J. Chem. Phys. 1972, 56, 976. (b) Chapps, G. D.; McCann, S. W.; Wickman, H. H.; Sherwood, R. C. J. Chem. Phys. 1974, 60, 990. (c) DeFotis, G. C.; Palacio, F.; O’Conners, C. J.; Bhatia,

S. N.; Carlin, R. L. J. Am. Chem. Soc. 1977, 99, 8314.

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Chapter 1

Magnetic Molecules

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Chapter 1

Magnetic Molecules

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Chapter 2

Theoretical Background

This chapter describes the theoretical background of the determination of magnetic exchange coupling constant from first principle calculations. An N-electron spin Hamiltonian is formulated for diradicals having non-degenerate highest occupied molecular orbitals. At first, energy expressions are obtained for singlet, broken-symmetry and triplet single-determinant wave functions of unrestricted Hartree-Fock treatment. Total energy values for the two-determinant singlet and triplet configurations that can be obtained from a self-consistent-field treatment are determined next by using the orbital perturbation theory. This leads to an energy ordering, which is expected to be valid also in an unrestricted Hartree-Fock Kohn-Sham treatment. The spin Hamiltonian is based on this ordering. Using the spin Hamiltonian, we obtain an expression for the energy differences from which the Yamaguchi and GND formula for J can be easily obtained.

Chapter 2

Theoretical Background

2.1. Introduction The interaction between two magnetic sites A and B in a diradical species is usually expressed by the Heisenberg two-spin Hamiltonian

(2.1)

H=E

0

2

JS

A

S

B

B are the respective spin angular momentum operators for the monoradical

fragments. A positive sign of J indicates a ferromagnetic interaction, whereas a negative sign indicates an antiferromagnetic interaction. The eigenfunctions of the Heisenberg Hamiltonian are eigenfunctions of S 2 and S z where S is the total spin angular momentum, and J is directly related to the energy difference between the eigenstates. For a diradical, E(S=1) E(S=0 )= 2J. The two-spin description of magnetic interaction has been

extensively correlated with the electronic structure of diradical systems. 1 Recently a large number ab initio calculations have been performed to evaluate J. 2 A proper mapping between the Heisenberg spin eigenstates and the electronic states is necessitated for the above procedure. This is true in principle but computationally very expensive. An alternative approach has been proposed by Noodleman so as to reliably compute the magnetic exchange coupling constant by density functional theory with less computational effort. 3 The spin polarized, unrestricted formalism and a broken-symmetry (BS) solution for

where

S

A

and

S

ˆ

the lowest spin-state are required in this method. The BS state is not an eigenstate of H . It is an equal mixture of singlet and triplet states. The coupling constant can be written as

J =

( E

BS

E

T

2

)

1

+

S

ab

(2.2)

where

solution. Eq. (2.2) is valid for the S=1/2 interacting spins. The quantity E BS is the energy of

the BS solution and

S ab

is the overlap integral between the spatial part of α and β orbitals in the BS

E T

is the energy of the triplet state in the unrestricted formalism using

the BS orbitals. In a single-determinant approach,

E can be approximated by the energy of

T

the true triplet state (

state.

E

T

E

T

) because of the very less spin contamination in the high spin

It is observed in literature that Eq. (2.2) is used in the strongly localized or orthogonal

limit where S 0 as well as the strongly delocalized limit where S 1. The current

ab

ab

literature is full of controversy regarding the choice of limit. Generally, in density functional

Chapter 2

Theoretical Background

(DFT) based calculations the magnetic orbitals are more delocalized than those obtained from the unrestricted Hartree-Fock (UHF) calculations, and some of the authors have recommended the use of Eq. (2.2) also in the strongly delocalized limit. 4 However, Bencini et al. have argued that Eq. (2.2) is to be restricted to the strongly localized limit. 5 It has also been concluded that the limit should be chosen on the basis of the proximity of calculated and experimental values, rather than a consideration of rigorous theoretical complications. 6 Illas et al. 7 have shown that the most often-quoted trend concerning the much larger degree of delocalization of magnetic orbitals obtained from DFT as opposed to UHF is not fully justified. They have recommended the use of the strongly localized limit for the general cases. In the strongly delocalized limit, Equation (2.2) becomes

(2.3)

In this situation singlet becomes degenerate with the broken-symmetry state which does not have any scientific evidence. Despite these problems and several other deficiencies in DFT as recently mentioned by several authors, Eq. (2.3) produced very impressive numerical results for some systems by using the so-called B3LYP exchange correlation functional treatment. 9 A large literature is found on this issue. 10 The following spin projected equations are commonly used in the investigation of J in different circumstances:

(i) the GND equation 11,12

2J E E .

BS

T

J (1)

=

DFT

(E

BS

DFT

E

T

)

 

(ii) the Bencini-Ruiz equation 13,14

 

S

max

2

 
 

J (2)

=

DFT

(E

LS

DFT

E

T

)

S

max

(

S

max

+

1)

 

(iii) the Yamaguchi equation 15

J

(3)

DFT

(E

BS

DFT

E

T

) .

= <

S

2

> −<

T

S

2

>

B S

 

(2.4)

(2.5)

(2.6)

To settle the controversy in the choice of the correct expression for J, Neese has recently analyzed the two-orbital system in CI and BS languages. 16 He has advocated the use of the corresponding orbital transformation (COT) due to Amos and Hall 17 to determine the non-

Chapter 2

Theoretical Background

orthogonal, ‘valence-bond’-like magnetic orbital pairs. It is evident that BS is not the only way to approach the problem of magnetic exchange coupling at DFT level. Recently Filatov et al. 9a-b proposed a methodology based on the Restricted Ensemble Khon-Sham formalism which deals directly with spin eigenfunctions. The procedure suffers from the strong dependence of exchange interaction with the exchange correlation potential. We find that there are two theoretical aspects involved here. First, the existing literature is based on the interpretation of the N-electron spin in the two-electron spin picture, that is, from an attempt to provide an interpretation of the calculated results for an N-electron system in terms of the Heisenberg two-spin Hamiltonian given by Eq. (2.1). The second aspect deals with the nature of the wave function. An unrestricted procedure basically relies on a single- determinantal wave function as the ground state configuration. The so-called BS approach is based on the single determinant. Therefore, any analysis of the results computed by the BS method must be based on such wave functions. Complications would still arise when the highest occupied molecular orbitals (HOMO) are degenerate. This work is on diradicals with non-degenerate HOMOs.

2.2. Theoretical background

The Heisenberg spin Hamiltonian is an effective Hamiltonian. It is normally written with a base line that equals the energy of the lowest spin state. For a diradical, the lowest spin state is a singlet. Nevertheless, a diradical is generally based on a pair of non-bonding orbitals which implies that the highest occupied molecular orbitals (HOMO) would be either non-degenerate (the single determinant representation) or degenerate. From two electrons occupying four spin orbitals corresponding to a pair of HOMOs, it is possible to build a set of triply degenerate configurations (triplet) and three singlet configurations. Therefore, one needs to identify the singlet that forms the base line.

2.2.1. Single determinant approach The single determinants for the singlet (S), broken-symmetry (B) and triplet (T) states in the unrestricted formalism are written as

Ψ S1 =||η 1 (r 1 )α(s 1 ) η / 1 (r 2 )β(s 2 )

Ψ S2 =||η ~ 1 (r 1 )α(s 1 ) η ~ / 1 (r 2 )β(s 2 )

η N/2 (r N1 )α(s N1 ) η / N/2 (r N )β(s N )||,

η ~ N/2+1 (r N1 )α(s N1 ) η ~ / N/2+1 (r N )β(s N )||,

Chapter 2

Theoretical Background

Ψ B1 =||ζ 1 (r 1 )α(s 1 ) ζ / 1 (r 2 )β(s 2 )

Ψ B2 =||ζ / 1 (r 1 )α(s 1 ) ζ 1 (r 2 )β(s 2 )

Ψ T1 =||ξ 1 (r 1 )α(s 1 ) ξ / 1 (r 2 )β(s 2 )

Ψ T2 =||ξ / 1 (r 1 )α(s 1 ) ξ 1 (r 2 )β(s 2 )

ζ N/2 (r N1 )α(s N1 ) ζ / N/2+1 (r N )β(s N )||, (2.7)

ζ / N/2+1 (r N1 )α(s N1 ) ζ N/2 (r N )β(s N )||,

ξ N/2 (r N1 )α(s N1 ) ξ N/2+1 (r N )α(s N )||,

ξ N/2 (r N1 )β(s N1 ) ξ N/2+1 (r N )β(s N )||.

In this work, we do not explicitly consider the density functional treatment as was done by Ginsberg, Noodleman and Davidson. Instead, we put forward a new spin Hamiltonian that is valid for N electrons. It holds so long as the single determinant picture is retained, the HOMOs are nondegenerate, and the energy ordering for the lowest six states, three singlets and a triplet, remains intact. The spatial orbitals ηs are mutually orthogonal and

similarly η / s are mutually orthogonal. The orbitals ηs are not necessarily orthogonal to η / s.

These sets {η} and {η / } are strictly determined from the unrestricted calculation. Similarly,

ζs are mutually orthogonal, ζ / s are also mutually orthogonal, but ζs need not be orthogonal

to ζ / s, and the sets {ζ} and {ζ / } are obtained from the BS calculations. The same situation is

valid for the triplet orbitals belonging to the sets {ξ} and {ξ / }. The sets {η}, {η ~ }, {ζ} and

{ξ} are in general somewhat different in the valence domain. Similarly, the sets {η / }, {η ~ / },

{ζ / }and {ξ / } differ from each other in the valence sector. The single determinant energy expectation values are

where

EE

S

1

=+

core

S 1

+

[

h

(

N

N /2

1

a = 1

+ J

(

N

/ 2)

αα

,

(

N

/ 2)

+

h

(

N

/ 2)

β

,

(

N

/ 2)

β

]

[{

JKJ

aN

αα

,

(

/ 2)

−+

(

aN

/ 2)

ααβα

,

(

aN

,

/ 2)

}

+

{

JKJ

β

aN

,

(

/ 2)

β

−+

β

aN

,

(

/ 2)

βα

(

aN

,

/2)

β

/ 2)

α

,

(N /2)β

}]

E

S 1

core

=

N /2

1

+

a = 1

1

2

(

hh

αα

a

,

a

+

a

β β

,

a

)

N

/2

1

N

/2

1

∑ ∑

a

=

1

b

=

1

(

JKJJKJ

ab

αα

,

ab

αα

,

++−

α β

ab

,

β β

ab

,

β β

ab

,

+

We similarly write

βα

ab

,

).

(2.8)

(2.9)

Chapter 2

Theoretical Background

EE

S

2

=+

core

S 2

+

[

h

]

JKJ

h

(

N

/ 2

+

(

N

/ 2

[{

1)

++

(

αα

,

(

aN

α

,

N

/ 2

1)

++

,

1)

β

(

N

/ 2

1)

β

N /2

1

a = 1

/ 2

+

1)

α

−+

(

aN

α

,

/ 2

+

1)

αβ

(

aN

,

/ 2

+

1)

α

}

+ J

(

N

+

/ 2

{

JKJ

/ 2

+

1)

β

−+

β

aN

,

(

/ 2

+

1)

β

aN

,

(

βα

(

aN

,

+

1)

α

,

(

N

/ 2

+

1)

β

,

/ 2

+

1)

β

EE

=

1

B

BB

1

=

E

B

2

=+ ′

Eh

core

[

(

N

N /2

a = 1

/

+

+ J

( N

+

h

(

N

/ 2

+

1)

β

,

(

N

/ 2

+

1)

β

]

−+′′

/ 2)

1

αα

,

[{

(

N

/ 2)

JKJ

aN

αα

,

(

/ 2)

(

aN

/ 2)

ααβα

,

(

aN

,

/ 2)

+ { JKJ

β

aN

,

(

/ 2

+

1)

β

β

aN

,

(

/ 2

+

1)

βα

(

aN

,

/ 2)

α

,

(

N

/ 2

+ 1)

β

,

−+′′

}

/ 2

+

1)

and

EE

=

TT

1

=

E

T

2

=+ [

core

(

N

Eh

T 1

′′

+

+

/ 2)

N /2

αα

,

(

N

/ 2)

1

+ h ′′

(

N

/ 2)

β

,

(

N

/ 2)

β

]

a = 1

[{

JKJ

aN

αα

,

(

/2)

(

aN

/2)

′′

−+′′

′′

ααβα

,

(

aN

,

/2)

(

J

+ { JKJ ′′ −+′′ ′′

,

// NN / 2)

aN

α

(

+

1)

+

(

/ 2

/ 2

(

αα

,

1)

α

K

//

(

N

(

aN

α

,

/ 2)

α

,

(

/ 2

+

1)

αβ

(

aN

,

N

/ 2

+

1)

α

)

β

}

/ 2

} ]

}]

+

1)

α

}]

(2.10)

(2.11)

(2.12)

where the tilde signs and the primes have been used to indicate that the integrals over the S1, S2, B and T orbitals are in general different from each other.

2.2.2. Two-determinant configurations

A linear combination of the BS determinants produces an approximation to the Ms = 0

component of triplet state

Ψ T3 = 2 1/2 (Ψ B1 +Ψ B2 )

(2.13)

with M S = 0 and similarly an approximation to the third singlet state

Ψ S3 = 2 1/2 (Ψ B1 −Ψ B2 ).

The corresponding energy values are

and

E T 3

/

= E

B

K

/

(2.14)

(2.15)

Chapter 2

Theoretical Background

E S 3

= E

B

core

/

|2

where the quantity K / is written as

/

1

KBB

=<

core

+ K

> K

/

(

K

(

NN / 2),(

/ 2

+

1)

=<

ςς

N

/ 2

N

N

/ 2

/ 2),(

N

+

1

|

ς

/ 2 + 1)

+

/ 2

N

1

,

ς

N

/ 2

> .

(2.16)

(2.17)

In a two-configuration self-consistent-field (TCSCF) process, the orbitals in Ψ T3 (and Ψ S3 )

would undergo relaxation to some extent to form configuration Ψ T3 (and Ψ S3 ) such that E T3

changes into E T3 that is equal to E T