Selective Formation of a Mixed-Valence State from Linearly Bridged Oligo(aromatic diamines): Drastic Structural Change into a Folded Columnar Stack for Half-filled Polycations

Wataru Nojo, Yusuke Ishigaki, Takashi Takeda, Tomoyuki Akutagawa, Takanori Suzuki

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)

Abstract

A method to obtain an organic mixed-valence state with long-range delocalization is proposed, which enables the selective generation of half-filled (n/2-charged) polycations from linearly bridged oligomers with n electron-donating units. When π-extended phenylenediamine units are connected by meta-xylylene-type spacers, the resulting oligomers adopt non-folded structures in the neutral state owing to the non-conjugating and flexible nature of the spacer, whereas the structure shows a drastic change into a one-dimensional columnar stack upon oxidation to the corresponding half-filled polycations. Although they are nano-sized discrete molecules, they can mimic the electronic structure of crystalline organic conductors in a mixed-valence state. The key for the oligomer design is adoption of the best-matched spacer that facilitates formation of the singly charged pimer in the dichromophoric system whereas the corresponding doubly charged π-dimer is disfavored.

Original languageEnglish
Pages (from-to)7759-7765
Number of pages7
JournalChemistry - A European Journal
Volume25
Issue number32
DOIs
Publication statusPublished - 2019 Jun 7

Keywords

  • cation radicals
  • electrochemical oxidation
  • indolocarbazole
  • multielectron transfer
  • polycations

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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