Density functional theory studies on the structures and electronic communication of meso-ferrocenylporphyrins: Long range orbital coupling via porphyrin core

Zhang, Lijuan; Qi, Dongdong; Zhang, Yuexing; Bian, Yongzhong; Jiang, Jianzhuang

doi:10.1016/j.jmgm.2010.12.006

Cited by 31 publications

(19 citation statements)

References 43 publications

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“…The electron density difference between ground and excited states is the linear combination of various electron transition models. Also for the reason of time efficiency, only the electron transition models with the configuration larger than 2.0% are taken into account . The electron density difference map is plotted using the isovalue of 2.0 × 10 −4 e/au 3 .…”

Section: Methodology Validity and Computational Detailsmentioning

confidence: 99%

The electronic structures and charge transfer properties of tetra(naphthalene-dione)porphyrins and tetra(naphthalene-dithione)porphyrins as dye-sensitized solar cell skeleton

Jiang

2013

Int. J. Quantum Chem.

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The p‐π conjugation of tetra(naphthalene‐dione)porphyrins and tetra(naphthalene‐dithione)porphyrins is clarified on the basis of density functional theory studies. When carbonyl/thionyl is introduced, π bonds on the molecular skeleton become strong–weak alternated, and the conjugation transforms from “benzene‐type” to “butadiene‐type.” The unidirectional photon‐induced current associated with the p‐π conjugation enables the light‐harvesting efficiency of this kind of molecular skeleton reaches 90% in the range of 300–800 nm. Therefore, these compounds are ideal alternative for panchromatic dye‐sensitized solar cells. © 2013 Wiley Periodicals, Inc.

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Section: Methodology Validity and Computational Detailsmentioning

confidence: 99%

The electronic structures and charge transfer properties of tetra(naphthalene-dione)porphyrins and tetra(naphthalene-dithione)porphyrins as dye-sensitized solar cell skeleton

Jiang

2013

Int. J. Quantum Chem.

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“…[2][3][4][5][6][7] Despite the extensive experimental research for a series of sandwich-type bis(tetrapyrrole) rare earth multidecker complexes, 1,2 theoretical studies have been focused mainly on the monomeric tetrapyrrole derivatives. [8][9][10][11][12][13][14][15][16][17] Recently, the neutral and protonated staggered bis(phthalocyaninato) lanthanum/yttrium double-decker complexes were investigated at the levels of B3LYP/LanL2DZ and VWN-B-P/TZP. [18][19][20][21] However, there seems to be no theoretical investigation at a high level to systematically study the reduced, neutral, and oxidized forms of bis(phthalocyaninato) rare earth doubledecker complexes.…”

Section: Introductionmentioning

confidence: 99%

Conformational effects, molecular orbitals, and reaction activities of bis(phthalocyaninato) lanthanum double-deckers: Density functional theory calculations

Zhang

Wan

et al. 2011

Phys. Chem. Chem. Phys.

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The conformational effects on the frontier molecular orbital energy and stability for reduced, neutral, and oxidized bis(phthalocyaninato) lanthanum double-deckers have been revealed on the basis of density functional theory calculations. Calculation results indicate that the frontier orbital coupling degree changes along with the molecular conformation of the double-decker compound, first decreasing along with the increase of rotation angle β from 0 to 20° and then increasing along with the increase of rotation angle β from 20 to 45°. In addition, the stability for the three forms of double-decker changes in the same order, but first increasing and then decreasing along with the change of the rotation angle β in the range of 0 to 45° with a rotation energy barrier of (31.3 ± 3.1) kJ mol(-1) at 20°. This reveals that the rotation of the two phthalocyanine rings for the reduced, neutral, and oxidized bis(phthalocyaninato) lanthanum double-deckers are able to occur at room temperature. Nevertheless, the superior coordination reaction activity of the neutral bis(phthalocyaninato) lanthanum double-decker complex over their reduced form in forming sandwich-type tris(phthalocyaninato) lanthanum triple-decker compounds has also been clearly clarified on the basis of comparative calculations on the Fukui function of [La(Pc)(2)] and [La(Pc)(2)](-) using the DFT method. Fukui function analysis reveals the reaction center of the 18-electron-π-conjugated core in the bis(phthalocyaninato) lanthanum double-decker molecule against both electrophilic and radical attack. Nevertheless, the larger global chemical softness (S) for the neutral [La(Pc)(2)] than the reduced form [La(Pc)(2)](-) indicates the higher reaction activity of the former form over the latter one. This explains well the experimental findings that only the neutral instead of the reduced form of bis(tetrapyrrole) rare earth double-decker complexes, containing at least one phthalocyanine ligand, could be employed as starting materials towards the preparation of tris(tetrapyrrole) rare earth triple-decker complexes by a solution process.

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“…According to the current research results, the generalized gradient approximation (GGA) functional BP86 with the basis set 6-31+g(d, p) can make the computational results fit the experimental data well. [57][58][59][60][61][62] Synthesis General procedure for synthesis of 1. To a degassed solution of dipyrromethane (146.2 mg, 1 mmol), methyl 4-formylbenzoate (82.1 mg, 0.5 mmol), and aromatic aldehyde (0.5 mmol) in CH 2 Cl 2 (100 ml) was added F 3 CCOOH (0.6 mmol, 44 ml).…”

Section: Dft Calculation Methodsmentioning

confidence: 99%

Synthesis and characterization of simple trans-AB-porphyrins for dye-sensitized solar cells

Zhang

Feng

et al. 2013

New J. Chem.

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Density functional theory studies on the structures and electronic communication of meso-ferrocenylporphyrins: Long range orbital coupling via porphyrin core

Cited by 31 publications

References 43 publications

The electronic structures and charge transfer properties of tetra(naphthalene-dione)porphyrins and tetra(naphthalene-dithione)porphyrins as dye-sensitized solar cell skeleton

The electronic structures and charge transfer properties of tetra(naphthalene-dione)porphyrins and tetra(naphthalene-dithione)porphyrins as dye-sensitized solar cell skeleton

Conformational effects, molecular orbitals, and reaction activities of bis(phthalocyaninato) lanthanum double-deckers: Density functional theory calculations

Synthesis and characterization of simple trans-AB-porphyrins for dye-sensitized solar cells

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