Hydrogen-bonded maleate counter anions in tetrathiafulvalene crystals

Subbalakshmi Jayanty, Tomoyuki Akutagawa, Takayoshi Nakamura

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)

Abstract

Intramolecular and/or intermolecular hydrogen-bonded maleate (HMA -) monoanions were introduced into cation radical salts of tetrathiafulvalene (TTF), forming three kinds of crystals: (TTF +)(H2MA)(HMA -) (1), (TTF +) 3(HMA -) 3(CH 3OH)(H 2O) 0.5 (2), and (TTF +) 3(TTF 0) 5(HMA -) 3 (3). In crystals 1 and 2, the monovalent TTF + cation formed a strong π-dimer of (TTF +) 2 and a π-trimer of (TTF +) 3, respectively. In crystal 3, a non-uniform π-stack of TTF 0 and TTF + was formed, which was further surrounded by neutral TTF through S⋯S and S⋯π interactions, forming a cylindrical TTF 0 array around the π-stack. A charge-separated electronic state of (TTF +) 3(TTF 0) 5(HMA -) 3 in crystal 3 was observed in the Raman spectra. Crystal 3 showed a semiconducting temperature dependent behavior with a room temperature conductivity of 3 × 10 -3 S cm -1, which was six orders of magnitude higher than those of crystals 1 and 2. The protonated state of the (H2MA)(HMA -) anion in crystal 1 was representative of an (HMA -⋯H +⋯HMA -) dimer, where the bridging proton between the two HMA - anions was located at the midpoint between the two oxygen sites. A very strong intramolecular symmetrical O-H⋯O - hydrogen-bonding interaction was observed in crystals 1-3 according to potential energy calculations of proton coordination in the O-H⋯O - hydrogen bonding.

Original languageEnglish
Pages (from-to)3875-3881
Number of pages7
JournalCrystEngComm
Volume14
Issue number11
DOIs
Publication statusPublished - 2012 Jun 7

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

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