Effect of peripheral fused ring substitution on the optical spectroscopy and electronic structure of metal phthalocyanine complexes

Wadzanai Chidawanyika, John MacK, Soji Shimizu, Nagao Kobayashi, Tebello Nyokong

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)

Abstract

In this paper the impact of peripheral substitution with a strongly withdrawing fused ring group on the optical spectroscopy of a metal phthalocyanine complex is analyzed. We report the synthesis of [9 (or 10), 16 (or 17), 23 (or 24)-tri-tert-butylimidophthalocyaninato]zinc(II) (ZnttbIPc), which should eventually prove to be a useful precursor for forming dimeric compounds. The electronic structure is analyzed through a detailed analysis of the UV-visible absorption and magnetic circular dichroism spectra and time-dependent density functional theory calculations. Other than a marked splitting of the Q band, the spectrum is broadly similar to that of ZnPc in terms of the main π → π* electronic bands. The vibrational bands differ markedly in the Q band region when an imido group is added to ligand periphery, relative to what is observed in the case of zinc mononaphthotribenzotetraazaporphyrin (Zn3B1N) with an additional fused benzene ring. The absorption and emission spectra lack mirror symmetry as is the case with ZnPc and thus provide possible evidence for a second set of electronic origins in the Q band region arising from n → π* rather then π → π* transitions.

Original languageEnglish
Pages (from-to)1053-1062
Number of pages10
JournalJournal of Porphyrins and Phthalocyanines
Volume13
Issue number10
DOIs
Publication statusPublished - 2009 Oct

Keywords

  • MCD spectrocopy
  • TD-DFT calculations

ASJC Scopus subject areas

  • Chemistry(all)

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