Design a better metalloporphyrin semiconductor: A theoretical studies on the effect of

substituents and central ions

,
Fadjar Mulya , Grisani A. Santoso, Hafiz A. Aziz, and Harno D. Pranowo

Citation: AIP Conference Proceedings 1755, 080006 (2016); doi: 10.1063/1.4958514

View online: http://dx.doi.org/10.1063/1.4958514
View Table of Contents: http://aip.scitation.org/toc/apc/1755/1
Published by the American Institute of Physics
 Design a Better Metalloporphyrin Semiconductor: A
Theoretical Studies on the Effect of Substituents and
Central Ions
Fadjar Mulya1, 2,a), Grisani A. Santoso1, 2, Hafiz A. Aziz1, 2, Harno D. Pranowo1, 2
1
Austrian-Indonesian Centre for Computational Chemistry, Universitas Gadjah Mada,
Sekip Utara, Yogyakarta, 55281, Indonesia
2
Department of Chemistry, Faculty of Mathematic and Natural Sciences, Universitas Gadjah Mada,
Sekip Utara, Yogyakarta, 55281, Indonesia
a)
corresponding author: fadjar.mulya@mail.ugm.ac.id

Abstract. We have studied the effects on central metal and substituent group on the complex compounds
metalloporphyrin as a semiconductor material. Cd2+, Hg2+, and Pt2+ were chosen as the central metal to see the effect of
the elements on the nature of the group and the same period and reviewed the effect of substituent groups pull and push
the electrons to the electronic properties of complex metalloporphyrin. The DFT/B3LYP/LANL2DZ and TD-DFT
calculation were used to generate the optimized structure of, electronic and photophysical properties. The parameter is an
Eg complex compound, DOS, and electronic absorption spectra. The calculations showed electron donating complexes
tend to be better as a semiconductor because it lowers Eg complex compounds metalloporphyrin, NH2 group gave the
smallest Eg compared to other groups.

INTRODUCTION
Porphyrin and metal-porphyrin complexes were common in nature and had been a considerable interest between
material scientist because their electronic and optical properties. Many researches both theoretically and
experimentally had been performed to study their structure, properties and performance [1-7].
The structure of porphyrin itself was planar with D2h symmetry (D4h for its ion). On the other hand, the structure
of metal-porphyrin was varied from planar to concave shape depending on the substituent group, the existence of
another ligand, and the size of the metal itself [8-10].
Porphyrin and metalloporphyrin properties itself were interests to study. Some of their properties were optical
activity, catalytic properties, and semiconductor properties. Some metal porphyrin can even designed to be dye-
sensitized solar cells material because of its low HOMO-LUMO energy difference, and high density of states above
Fermi Level [11-14].
The semiconductor properties of metalloporphyrin were quite an interest because they were so common in nature
and present in many forms. From molecular design itself, it was evident that there was a link between metal-
porphyrin composition and structure with their properties. There were quite a few studies on the effect of different
metal affecting the properties of metal porphyrin as a semiconductor. Some of the studies were also concerned the
effect of substituent on the ring. But one thing common in those studies was the asymmetrically substituted
porphyrin. There were some studies on symmetrically substituted porphyrin, but none of them systematically
investigated the effect of both substituents and central ions simultaneously on the electronic and photo-physical
properties [15-18].
In this study, the effect of different central ions and substituents is discussed for various metalloporphyrin
complexes. The central ions selected in this study were Cd(II), Hg(II) and Pt(II). The substituents selected in this
study were F, I, NO2, NH2, CH3 and H as a control variable.

Advances of Science and Technology for Society

AIP Conf. Proc. 1755, 080006-1080006-5; doi: 10.1063/1.4958514
Published by AIP Publishing. 978-0-7354-1413-6/$30.00

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 COMPUTATIONAL DETAILS
The electronic structure was calculated using the Kohn-Shams density functional theory (DFT) method, B3LYP
exchange-correlation function and LANL2DZ basis set [19-22]. The UV-Vis spectra were calculated using TD-
DFT/B3LYP/LANDL2DZ (N=10) from the optimized structure. Both calculations were performed using Gaussian
09 packaged software [23]. The density of states was calculated on the optimized structure using Gauss Sum 2.2.5 software
[24].

RESULTS AND DISCUSSION

Electronic structure
The electronic structure of chemical species related to its electron density. In metalloporphyrin complexes, the
electronic structure is directly affected by the central ions and the substituents that were attached to the porphyrin
ring. The effect of central ions and substituents to the electronic structure of the metalloporphyrin complexes is
shown in Table 1 and Fig. 1.
TABLE 1. Orbital energy level and band gaps of the complex in eV.
Substituent Cd Hg Pt
Group HOMO LUMO Eg HOMO LUMO Eg HOMO LUMO Eg
H -5.37 -2.51 2.86 -5.34 -2.49 2.85 -5.65 -2.47 3.18
F -5.79 -3.16 2.63 -5.76 -3.14 2.62 -6.01 -3.09 3.01
I -5.69 -3.14 2.55 -5.67 -3.14 2.53 -5.93 -3.03 2.9
NO2 -7.02 -4.18 2.84 -7.13 -4.53 2.6 -4.58 -1.62 2.96
NH2 -3.47 -1.67 1.8 -3.46 -1.67 1.79 -3.76 -1.65 2.11
CH3 -4.9 -2.33 2.57 -4.87 -2.32 2.55 -5.16 -2.23 2.93

HOMO-LUMO energy gap (band gap) is the physical properties of a molecule that can create potential for
interacting electrons in energy levels, the smaller the band gap value has implications for the ease of electron
excitation so that the nature of the sensitivity to light (photosensitivity) will be higher.
Table 1 and Fig. 1 showed the HOMO-LUMO energy gap of metalloporphyrin complexes. The previous study
performed by Berbee and Kuznetsov [25] proved that electron donating group will destabilize the orbitals resulting
in the decrease of band gap energy and increase of orbitals energy. Table 1 also showed that the band gap energy
average increased in the series HgP-R - CdP-R - PtP-R. This was caused by the stabilization energy and
occupancy of the orbitals. In CdP-R and HgP-R, band gap energy was defined by the excitation energy from
to s orbital. While in PtP-R, the band gap energy was defined by the excitation energy from to orbital
resulting on the increase of band gap energy. Very high band gap energy in semiconductor means the electron will
need more energy to be excited, therefore making the material become less efficient as a semiconducting material.
Very lowband gap on the other hand will cause the electron exctitation hard to control and hard to use. Therefore,
control of the band gap energy value is needed to design a better semiconductor.

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 FIGURE 1. HOMOs, LUMOs, and energy gaps of complexes

Density of states
The density of states (DOS) is describing the number of states that can be occupied by an electron at an energy
level per unit volume.
TABLE 2. Abundance DOS on the HOMO and LUMO in the complex
Substituent DOS CdP-R DOS HgP-R DOS PtP-R
Group HOMO LUMO HOMO LUMO HOMO LUMO
H 0.98659 1.96465 1.00059 1.99658 1.98166 1.99224
F 0.98093 1.93417 0.99997 1.99945 0.99651 1.95610
I 0.98874 1.96930 0.82106 1.99861 0.99213 1.96894
NO2 1.01519 1.95118 1.57133 1.99816 0.99936 1.98111
NH2 0.99786 1.98562 0.99602 1.99672 0.99940 1.98579
CH3 0.99725 1.95807 0.99969 1.99343 0.98386 1.99195

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 Table 2 showed that DOS abundances on the LUMO energy level of the complexes are not affected by either the
central ions nor the substituents. DOS abundance on the HOMO energy level, on the other hand, are affected by the
substituents. The complexes with the electron withdrawing group have higher DOS abundance suggesting that
electron withdrawing group increase number of states or decrease amount of volume, therefore increasing the DOS
abundance of the complexes. The increase of DOS abundance in HOMO, in turn, would increase the probability of
the electron-hole recombination in the complexes that will affect the.

UV-Vis Spectra
TABLE 3. The absorption spectra of complex
Substituent max
Group Cd Hg Pt
H 360.75 365.97 350.92
I 579.5 399.11 516.62
F 543.79 368.46 355.31
NO2 539.31 456.01 627.33
CH3 377.95 384.33 369.12
NH2 701.59 367.43 622.35

UV-Vis spectra is a photo-physical property of a molecule that arises from an absorption of light by an electron
that excited to higher energy level. In semiconductor science, electronic absorption spectra are one of the parameters
that are used to determined the performance of a semiconductor material. The semiconductor material that can
absorp light at the visible light range has better performance than the materials that can only absorp the UV light
range.
Table. 3 showed the data of peak of the metalloporphyrin complexes electronic absorption spectra. All
complexes with substituent exhibit a red shift of the peak relatively to the control variable. This variation applies to
Woodward Fischer rule. The complexes with electron withdrawing group tend to have a higher wavelength.
Therefore, it has a bigger red shift. The different in the red shift is caused by the stability of the orbital. Stabil orbital
tend to have higher wavelength resulting greater red shift which results in the increase of max HgP-R - PtP-R -
CdP-R in series.

CONCLUSION
We have performed DFT/TD-DFT calculation
x The bandgap energy of complexes was decreasing in the series PtP-R - CdP-R - HgP-R and the complexes
with electron donating group tended to have smaller bandgap energy.
x The density of states of the complexes in LUMO was not affected by the substituents nor the central ions while
the density of states in HOMO tended to increase in the series of CdP-R-HgP-R - PtP-R.
x The peak of electronic absorption spectra was increasing in the series HgP-R - PtP-R - CdP-R and the
complexes with electron withdrawing group tended to have a higher wavelength.

ACKNOWLEDGMENT
We are grateful for Austrian-Indonesian Centre for Computational Chemistry, Gadjah Mada University, for
computer time and facilities.

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