Excited-State Aromaticity of Gold(III) Hexaphyrins and Metalation Effect Investigated by Time-Resolved Electronic and Vibrational Spectroscopy

Jinseok Kim, Juwon Oh, Takanori Soya, Tomoki Yoneda, Seongchul Park, Manho Lim, Atsuhiro Osuka, Dongho Kim

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Expanded porphyrins with appropriate metalation provide an excellent opportunity to study excited-state aromaticity. The coordinated metal allows the excited-state aromaticity in the triplet state to be detected through the heavy-atom effect, but other metalation effects on the excited-state aromaticity were ambiguous. Herein, the excited-state aromaticity of gold(III) hexaphyrins through the relaxation dynamics was revealed via electronic and vibrational spectroscopy. The SQ states of gold [26]- and [28]-hexaphyrins showed interconvertible absorption and IR spectra with those of counterparts in the ground-state, indicating aromaticity reversal. Furthermore, while the T1 states of gold [28]-hexaphyrins also exhibited reversed aromaticity according to Baird's rule, the ligand-to-metal charge-transfer state of gold [26]-hexaphyrins contributed by the gold metal showed non-aromatic features arising from the odd-number of π-electrons.

Original languageEnglish
Pages (from-to)5129-5134
Number of pages6
JournalAngewandte Chemie - International Edition
Volume59
Issue number13
DOIs
Publication statusPublished - 2020 Mar 23

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

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