Application of the perimeter model to the assignment of the electronic absorption spectra of gold(III) hexaphyrins with [4n + 2] and [4n] π-electron systems

Atsuya Muranaka, Osamu Matsushita, Kengo Yoshida, Shigeki Mori, Masaaki Suzuki, Taniyuki Furuyama, Masanobu Uchiyama, Atsuhiro Osuka, Nagao Kobayashi

Research output: Contribution to journalArticlepeer-review

36 Citations (Scopus)

Abstract

The electronic excited states of two forms of meso- hexakis(pentafluorophenyl)-substituted gold(III) hexaphyrin(1.1.1.1.1.1) have been investigated by density functional calculations and magnetic circular dichroism (MCD) spectroscopy, in order to assign their low-energy excited singlet states. We found that the perimeter model can be successfully applied to the interpretation of the electronic states. In the case of the neutral forms (Au2-N, Au-N), the absorption bands observed in the NIR and visible region can be assigned to π-π* transitions referred to as the L and B bands, respectively, analogous to the Q and Soret bands of regular porphyrins. In marked contrast with the neutral forms, the absorption bands of the reduced forms (Au2-R and Au-R) are attributed to π-π* transitions involving six frontier molecular π orbitais. By applying the 4N-electron perimeter model, the six orbitais are labeled as h-, h+, s-, S+, l-, and l+, while the observed absorption bands can be assigned to the S, N1, N 2, P1, and P2 transitions, in order of increasing energy.

Original languageEnglish
Pages (from-to)3744-3751
Number of pages8
JournalChemistry - A European Journal
Volume15
Issue number15
DOIs
Publication statusPublished - 2009 Apr 6

Keywords

  • Ab initio calculations
  • Electronic structure
  • Magnetic properties
  • Porphyrinoids

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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