9,9'-bi(xanthene)-type hexaphenylethane derivatives as advanced organic electrochromic systems

Takanori Suzuki, Yusuke Ishigaki, Masaki Takata, Jun Ichi Nishida, Takanori Fukushima

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)

Abstract

9-Phenylxanthenyl radical can undergo facile C-C bond formation at C9-position when the two units of the radical are connected at C2'-positions to give stable intramolecular dimer (1), which is a clamped hexaphenylethane derivative with an elongated C-C bond. The newly formed bond in 1 can be cleaved easily upon two-electron oxidation to give bis(9-xanthenylium)-type dication (22+), from which the diradical is generated upon two-electron reduction. This review account describes the dynamic redox ("dyrex") pair of colorless 1 and yellow-orange 22+, which provides a versatile scaffold to develop multi-functional electrochromic systems. Both of 1 and 22+ are sterically challenged molecules and thus adopt characteristic skewed geometries. Electrochiroptical response was realized by suppressing the chiral inversion of helicity in 1 and axial chirality in 22+ whereas redox-induced fluorescence switching was attained by attaching the fluorophore whose emission is quenched by xanthenylium in 22+ but not by spiro(xanthene) unit in 1. By the molecular design that allows intramolecular chiral transmission, the spectral changes were also induced by the external stimuli (e.g. heat, pH) other than redox input, which made it possible to construct less well-explored multi-input-multi-output response systems. More advanced functions could be endowed, such as chiral redox memory or reversible O2-storage, by further modification of the prototype.

Original languageEnglish
Pages (from-to)419-450
Number of pages32
JournalHeterocycles
Volume102
Issue number3
DOIs
Publication statusPublished - 2021
Externally publishedYes

ASJC Scopus subject areas

  • Analytical Chemistry
  • Pharmacology
  • Organic Chemistry

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