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 |
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| Authors: | Yuexing Zhang Dongdong Qi Xue Cai Jianzhuang Jiang |
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| Institution: | 1. Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China;2. Department of Chemistry, Shandong University, Jinan 250100, China;3. Department of Chemistry, Mudanjiang Normal College, Mudanjiang 157012, China |
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| Abstract: | 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‐OCH3)4] (4), Y(Pc)Pc(α‐OCH3)8] (5), and Y(Pc)Pc(β‐OCH3)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 |
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| Keywords: | electronic absorption spectra phthalocyanine porphyrin rare earth double‐decker density functional theory |
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