DFT/TD-DFT molecular design of porphyrin analogues for use in dye-sensitized solar cells

Balanay, Mannix P.; Kim, Dong Hee

doi:10.1039/b806097e

Cited by 137 publications

(87 citation statements)

References 56 publications

(84 reference statements)

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“…[12][13][14]22 TD-DFT (B3LYP/6-31G(d)) calculations of zinc porphine (ZnP), have shown that the FMOs are well separated from other MOs and are the major contribution to the Q and B bands, in agreement with the four-orbital model. 23 In addition to this, the B band also contains a minor contribution from lower lying orbitals.…”

mentioning

confidence: 65%

“…3 However, the cost and limited availability of ruthenium, coupled with its undesirable environmental impact has led to investigation of organic based materials for DSSC applications [4][5][6][7][8][9][10] Porphyrins have a number of desirable properties for use in a DSSC and have attracted a great deal of attention. 4,[9][10][11][12][13][14][15] They are able to harvest light over a wide spectral range which is crucial for good DSSC performance. 9 The long-lived excited states 9,16 of porphyrins and efficient electron transfer into the conduction band of TiO 2 17 are also properties which make them effective DSSC dyes.…”

Section: Introductionmentioning

confidence: 99%

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A spectroscopic and DFT study of thiophene-substituted metalloporphyrins as dye-sensitized solar cell dyes

Lind

Gordon

Gambhir

et al. 2009

Phys. Chem. Chem. Phys.

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Officer, D. L. (2009). A spectroscopic and DFT study of thiophene-substituted metalloporphyrins as dye-sensitized solar cell dyes. Physical Chemistry Chemical Physics, 11 (27),[5598][5599][5600][5601][5602][5603][5604][5605][5606][5607] A spectroscopic and DFT study of thiophene-substituted metalloporphyrins as dye-sensitized solar cell dyes Abstract A combination of density functional theory calculations, electronic absorption and resonance Raman spectroscopy has been applied to a series of beta-substituted zinc porphyrins to elucidate how the substituent affects the electronic structure of the metalloporphyrin and assign the nature of electronic transitions in the visible region. The use of conjugated beta substituents invokes a large perturbation to both the nature and energy of the frontier molecular orbitals and results in the generation of additional molecular orbitals from the parent metalloporphyrin species. A complicated electronic absorption spectra is observed which can be rationalised by an extension of Goutermans' four-orbital model. The excitations involved in the visible transitions have been determined using resonance Raman spectroscopy. This has revealed that the B band retains much of its original nature and is centred largely on the porphyrin core. Additional electronic transitions invoke population of orbitals localised on the substituent chain. The nature of the electronic transitions depends heavily on the type of b substituent. The results of this investigation question some previously held beliefs for the rational design of metalloporphyrins for dye-sensitized solar cell applications. A combination of density functional theory calculations, electronic absorption and resonance Raman spectroscopy has been applied to a series of b-substituted zinc porphyrins to elucidate how the substituent affects the electronic structure of the metalloporphyrin and assign the nature of electronic transitions in the visible region. The use of conjugated b substituents invokes a large perturbation to both the nature and energy of the frontier molecular orbitals and results in the generation of additional molecular orbitals from the parent metalloporphyrin species. A complicated electronic absorption spectra is observed which can be rationalised by an extension of Goutermans' four-orbital model. The excitations involved in the visible transitions have been determined using resonance Raman spectroscopy. This has revealed that the B band retains much of its original nature and is centred largely on the porphyrin core. Additional electronic transitions invoke population of orbitals localised on the substituent chain. The nature of the electronic transitions depends heavily on the type of b substituent. The results of this investigation question some previously held beliefs for the rational design of metalloporphyrins for dye-sensitized solar cell applications.

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mentioning

confidence: 65%

Section: Introductionmentioning

confidence: 99%

A spectroscopic and DFT study of thiophene-substituted metalloporphyrins as dye-sensitized solar cell dyes

Lind

Gordon

Gambhir

et al. 2009

Phys. Chem. Chem. Phys.

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“…Molecular orbitals were visualized by GaussView 3.0 software. [33] The method has been widely used for geometry optimizations and electronic calculations of porphyrin derivatives due to its accuracy, [4,5,6,34,35] which was further validated by the very similar bond angles and lengths in the optimized structures of MTPP-AOP (M = 2H + , Zn 2+ , Cu 2+ ) and single-crystal structures.…”

Section: Photocurrent-voltage Measurementsmentioning

confidence: 99%

2‐(1‐Acetyl‐2‐oxopropyl)‐5,10,15,20‐tetraphenylporphyrin and Its Transition‐Metal Complexes

Dubey

Zhong

et al. 2011

Eur J Inorg Chem

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The 2-(1-acetyl-2-oxopropyl)-5,10,15,20-tetraphenylporphyrin free base (H 2 TPP-AOP) and its transition-metal complexes (MTPP-AOP, M = Cu 2+ , Zn 2+ ) have been synthesized. Single-crystal X-ray diffraction analysis revealed that the 1-acetyl-2-oxopropyl (AOP) group is attached to a β-pyrrolic position through the methylene group. The mean plane of the AOP is almost perpendicular to the porphyrin ring. The zinc(II) complex crystallizes as a five-coordinate species with one methanol/water solvate in the axial position, whereas the copper(II) complex is four-coordinate. These compounds exhibit strong absorption in the UV and visible regions. The fluorescence lifetimes are 1.85 and 8.0 ns for the free base

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“…As a model for nanocrystallinity the HOMO and LUMO energies of bare cluster (TiO 2 ) 38 are -7.23 and -4.1 eV, respectively, resulting in a E gap of 3.13 eV [26]. Generally energy gap more than 0.2 eV between the LUMO of the dye and the conduction band of the TiO 2 is necessary for effective electron injection [27].…”

Section: Geometriesmentioning

confidence: 99%

Synthesis, characterization and density functional theory study of low cost hydrazone sensitizers

Al‐Sehemi¹,

Irfan²,

Asiri³

et al. 2015

Bull. Chem. Soc. Eth.

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ABSTRACT. The 2-{4-[2-benzylidenehydrazino]phenyl}ethylene-1,1,2-tricarbonitrile (System 1), 2-{4-[2-(1-naphthylmethylene)hydrazino]phenyl}ethylene-1,1,2-tricarbonitrile (System 2) and 2-{4-[2-(9-anthrylmethylene)-hydrazino]phenyl}ethylene-1,1,2-tricarbonitrile (System 3) were synthesized by direct tricyanovinylation of hydrazones. The bathochromic shift in absorption spectra has been observed by increasing the solvent polarity. The FTIR spectra of these new dyes exhibited three important absorption bands. The first band centered near 3260 cm -1 in System 1 while 3208 cm -1 and 3211 cm -1 in System 2 and System 3 for the NH absorption, respectively. The second band is a sharp absorption band in the region of 2212-2209 cm -1 , which was attributed to the cyano group absorption. The third is an absorption band in the region of 1611-1603 cm -1 ascribed for the C=N. Density functional theory (DFT) calculation of relative energies, relative enthalpies and free energies shows that E isomers are the most stable except System 3 in which the most stable is Z isomers. The conformational energy profile shows two maxima near (-90 and 90 o ) while three local minima observed at (-180, 0 and 180) for N1-N2-C1-C2 torsional angle. The highest occupied molecular orbitals (HOMOs) are localized on the whole molecules while lowest unoccupied molecular orbitals (LUMOs) are distributed on the tricarbonitrile.

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DFT/TD-DFT molecular design of porphyrin analogues for use in dye-sensitized solar cells

Cited by 137 publications

References 56 publications

A spectroscopic and DFT study of thiophene-substituted metalloporphyrins as dye-sensitized solar cell dyes

A spectroscopic and DFT study of thiophene-substituted metalloporphyrins as dye-sensitized solar cell dyes

2‐(1‐Acetyl‐2‐oxopropyl)‐5,10,15,20‐tetraphenylporphyrin and Its Transition‐Metal Complexes

Synthesis, characterization and density functional theory study of low cost hydrazone sensitizers

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