Cationic π-Stacking Columns of Coronene Molecules with Fully Charged and Charge-Disproportionated States

Yukihiro Yoshida, Kazuhide Isomura, Mitsuhiko Maesato, Takashi Koretsune, Yoshiaki Nakano, Hideki Yamochi, Hideo Kishida, Gunzi Saito

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Electrochemical oxidation of a polycyclic aromatic hydrocarbon, coronene, with D6h symmetry in the presence of tetrahedral GaCl4- anions gave two cation salts, (coronene)(GaCl4) (1) and (coronene)5(GaCl4)2 (2), with unprecedented charge arrangements. Salt 1 involves π-stacking columns in a zigzag manner, which are composed of the crystallographically equivalent coronene monocations. First-principle calculations revealed that the dimerization of coronene cations gives rise to a band gap opening at the Fermi level, and thus, semiconducting behavior. On the other hand, in salt 2, two crystallographically independent coronene molecules (A and B) form π-stacking columns with an AABB repeating unit, which are flanked by another coronene molecule (C). The crystallographic features, such as interplanar distances and in-plane molecular distortions arising from the Jahn-Teller effect, as well as the first-principle calculations, strongly suggested the emergence of charge disproportionation within the π-stacking columns. As in the case of 1, the calculated band structure exhibits a band gap opening at the Fermi level, which corresponds to the observed semiconducting behavior.

Original languageEnglish
Pages (from-to)5994-6000
Number of pages7
JournalCrystal Growth and Design
Volume16
Issue number10
DOIs
Publication statusPublished - 2016 Oct 5
Externally publishedYes

ASJC Scopus subject areas

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

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