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

Yuexing Zhang, Dongdong Qi, Xue Cai, Jianzhuang Jiang*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

1 Scopus citations


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 theπ- π interaction between the two tetrapyrrole rings in bis(tetrapyrrole) rare earth(III) double-decker complexes because of its peculiar electronic transition nature.

Original languageEnglish (US)
Pages (from-to)1559-1564
Number of pages6
JournalInternational Journal of Quantum Chemistry
Issue number8
StatePublished - Jul 1 2010


  • Density functional theory
  • Double-decker
  • Electronic absorption spectra
  • Phthalocyanine
  • Porphyrin
  • Rare earth

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

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