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Nature of the near‐IR band in the electronic absorption spectra of neutral bis(tetrapyrrole) rare earth(III) complexes: Time‐dependent density functional theory calculations
Author(s) -
Zhang Yuexing,
Qi Dongdong,
Cai Xue,
Jiang Jianzhuang
Publication year - 2010
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22243
Subject(s) - tetrapyrrole , chemistry , density functional theory , homoleptic , electronic structure , homo/lumo , absorption spectroscopy , crystallography , computational chemistry , molecule , physics , metal , organic chemistry , quantum mechanics , enzyme
The nature of the near‐IR band in the electronic absorption spectra of bis(tetrapyrrole) rare earth(III) complexes Y(Pc) 2 (1), La(Pc) 2 (2), Y(Pc)(Por) (3), Y(Pc)[Pc(α‐OCH 3 ) 4 ] (4), Y(Pc)[Pc(α‐OCH 3 ) 8 ] (5), and Y(Pc)[Pc(β‐OCH 3 ) 8 ] (6) was studied on the basis of time‐dependent density functional theory (TD‐DFT) calculations. The electronic dipole moment along the z ‐axis in the electronic transition of the near‐IR band in all the studied neutral bis(tetrapyrrole) yttrium(III) and lanthanum(III) double‐deckers is well explained on the basis of the composition analysis of the orbitals involved. The electronic transition in the near‐IR band causes the reversion of the orbital orientation of one tetrapyrrole ring in both homoleptic and heteroleptic bis(tetrapyrrole) rare earth complexes and induces electron transfer from the tetrapyrrole ring with lower orbital energy to the other ring in the heteroleptic bis(tetrapyrrole) rare earth(III) complexes. The near‐IR band can work as an ideal characteristic absorption band to reflect the π–π interaction between the two tetrapyrrole rings in bis(tetrapyrrole) rare earth(III) double‐decker complexes because of its peculiar electronic transition nature. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010