Control of chromophore symmetry by positional isomerism of peripheral substituents

Soji Shimizu, Yu Haseba, Mariko Yamazaki, Genji Kumazawa, Nagao Kobayashi

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

The first example of the control of porphyrinoid chromophore symmetry based on the positional isomerism of peripheral substituents has been achieved by preparing tetraazaporphyrins (TAPs) with C4h, D2h, C 2v, and Cs symmetry due to the relative arrangement of peripheral tert-butylamino and cyano groups as push and pull substituents, respectively. The four structural isomers were successfully isolated and characterized by 1H NMR spectroscopy and X-ray crystallography. The band morphology in the Q-band region varies depending on the molecular symmetry due to the significant perturbation introduced into the chromophore by the push and pull substituents. The C4h and C2v isomers exhibit a single Q band, whereas the Q bands of the D2h and Cs isomers show a marked splitting. The magnetic circular dichroism spectra indicate that the push-pull TAPs retain the properties of the 16-membered 18π-electron perimeter generally observed for porphyrinoids. Theoretical calculations have demonstrated that the perturbation introduced by the substituents lowers the D4h symmetry of the parent TAP π-conjugated system, and this results in significant spectral changes. A novel approach to the fine-tuning of the spectral properties of porphyrinoids based on changes in the chromophore symmetry is described. Symmetry control: Control of porphyrinoid chromophore symmetry based on the positional isomerism of peripheral substituents has been achieved by preparing tetraazaporphyrins (TAPs) with C4h, D2h, C2v, and Cs symmetry as a result of the relative arrangement of peripheral substituents (see figure). A new approach to the fine-tuning of the spectral properties of porphyrinoids based on changes in the chromophore symmetry is described.

Original languageEnglish
Pages (from-to)4822-4828
Number of pages7
JournalChemistry - A European Journal
Volume20
Issue number16
DOIs
Publication statusPublished - Apr 14 2014
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

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