Redox-Dependent Transformation of a Hydrazinobuckybowl between Curved and Planar Geometries

Shuhei Higashibayashi, Palash Pandit, Rie Haruki, Shin Ichi Adachi, Reiji Kumai

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

A red-fluorescent heterobuckybowl with an embedded hydrazine structure was synthesized from a cyclobiphenothiazine derivative via a strained cyclobicarbazole. The hydrazinobuckybowl was found to possess bowl and twist structures in the neutral state, a shallow bowl structure in the monocation state, and a planar structure in the dication state by means of X-ray crystallographic analysis, DFT calculations, and a comparison of experimental and calculated 13C NMR chemical shifts. The hydrazinobuckybowl is the first buckybowl that changes its geometry between curved bowl/twist structures and a planar structure depending on the oxidation state. The drastic geometrical change was possible as a result of the presence of two heteroatoms in the bowl skeleton and the multiple reversible redox reactions of the compound. Owing to the two kinds of bowl and twist conformations, the bowl-inversion dynamics of the hydrazinobuckybowl were found to follow a triple-well potential model.

Original languageEnglish
Pages (from-to)10830-10834
Number of pages5
JournalAngewandte Chemie - International Edition
Volume55
Issue number36
DOIs
Publication statusPublished - 2016 Aug 26
Externally publishedYes

Keywords

  • cations
  • conformation analysis
  • heterobuckybowls
  • heterocycles
  • redox chemistry

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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