Jump to main content
Jump to site search


Charge-transfer complexes based on C2v-symmetric benzo[ghi]perylene: comparison of their dynamic and electronic properties with those of D6h-symmetric coronene

Author affiliations

Abstract

Single crystals of three neutral charge-transfer complexes and a cation radical salt based on a C2v-symmetric polycyclic aromatic hydrocarbon, benzo[ghi]perylene (bper), were obtained. The 1 : 1 complex with 7,7,8,8-tetracyanoquinodimethane (TCNQ) involves DA-type alternating π-columns, whereas the alternating π-columns in the 2 : 1 TCNQ complex are flanked by another bper molecule. The in-plane rotation of bper in the 1 : 1 complex was significantly suppressed compared with that of coronene in (coronene) (TCNQ), which is associated with the lower molecular symmetry of bper. Whereas the 3 : 1 TCNQ complex involves DDA-type alternating π-columns flanked by another bper molecule, bper molecules in the 3 : 1 cation radical salt with Mo6O192− have a columnar structure with a [101]-like charge-ordered pattern associated with intermolecular interactions in the bay region of bper. The dimerisation of charge-rich bper molecules results in an increased energy gap at the Fermi level, and consequently, semiconducting behaviour of the salt has a larger activation energy than that of the isostructural coronene salt in the partially charged state. The lower molecular symmetry of bper also affects the degeneracy of the frontier-orbitals; the energy difference between the HOMO and the HOMO−1 of bper is significantly larger than that of coronene, which is comparable to the intermolecular transfer integrals.

Graphical abstract: Charge-transfer complexes based on C2v-symmetric benzo[ghi]perylene: comparison of their dynamic and electronic properties with those of D6h-symmetric coronene

Back to tab navigation

Supplementary files

Publication details

The article was received on 16 Mar 2018, accepted on 13 Apr 2018 and first published on 16 Apr 2018


Article type: Research Article
DOI: 10.1039/C8QM00112J
Citation: Mater. Chem. Front., 2018, Advance Article
  •   Request permissions

    Charge-transfer complexes based on C2v-symmetric benzo[ghi]perylene: comparison of their dynamic and electronic properties with those of D6h-symmetric coronene

    Y. Yoshida, S. Tango, K. Isomura, Y. Nakamura, H. Kishida, T. Koretsune, M. Sakata, Y. Nakano, H. Yamochi and G. Saito, Mater. Chem. Front., 2018, Advance Article , DOI: 10.1039/C8QM00112J

Search articles by author

Spotlight

Advertisements