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Molecular Structure‐Property Relationships of the Asymmetric Thienoacenes: Naphtho[2,3‐ b ]thieno[2,3‐ d ]thiophene, Anthra[2,3‐ b ]thieno[2,3‐ d ]thiophene, and their Thienyl Derivatives
Author(s) -
Matsunaga Amane,
Ogawa Yuta,
Tamura Shigeki,
Yamamoto Kazuhiro,
Katagiri Hiroshi
Publication year - 2021
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.202101423
Subject(s) - thiophene , antiparallel (mathematics) , anthracene , crystal structure , intermolecular force , crystallography , chemistry , ring (chemistry) , molecule , stereochemistry , aromaticity , materials science , organic chemistry , physics , quantum mechanics , magnetic field
Polycyclic aromatic compounds are attractive candidates for organic semiconductor materials whose optical and charge transport properties are significantly influenced by the molecular and packing structures. In this work, we investigated the crystal structure and physical properties of asymmetric bent‐shaped thienoacenes, which have a thieno[3,2‐ b ]thiophene unit at the end of the fused aromatic ring core, and their thienyl extended‐type derivatives. Among the naphthalene‐based analogs, naphtho[2,3‐ b ]thieno[2,3‐ d ]thiophene and its thienyl derivative gave an antiparallel slip‐stack structure. In contrast, among the anthracene‐based analogs, anthra[2,3‐ b ]thieno[2,3‐ d ]thiophene produced an antiparallel slip‐stack structure, while its thienyl derivative gave a layered structure with a large molecular orbital overlap. In extended conjugated systems, molecular symmetry of the long axis and dispersion forces were improved, resulting in the formation of crystal structures with large intermolecular interactions. These results suggest the importance of both the extension and molecular symmetry of a conjugated system to controlling the molecular structure.