TY - JOUR
T1 - Charge-transfer complexes based on C2v-symmetric benzo[ghi]perylene
T2 - Comparison of their dynamic and electronic properties with those of D6h-symmetric coronene
AU - Yoshida, Yukihiro
AU - Tango, Shunsuke
AU - Isomura, Kazuhide
AU - Nakamura, Yuto
AU - Kishida, Hideo
AU - Koretsune, Takashi
AU - Sakata, Masafumi
AU - Nakano, Yoshiaki
AU - Yamochi, Hideki
AU - Saito, Gunzi
N1 - Funding Information:
This work was supported by the Japan Society for the Promotion of Science (JSPS) KAKENHI Grant Numbers JP25288041 and JP16H04139 (YY), JP16H00924 (TK), JP15K17901 and JP17H05153 (Y. Nakano), JP26288035 (HY), JP26110512 and JP16H00964 (HK), and JP23225005 (GS) and by JST PRESTO (TK). Theoretical calculations were partly performed at Research Center for Computational Science, Okazaki, Japan, and the SuperComputer System, Institute for Chemical Research, Kyoto University, Japan.
Publisher Copyright:
© The Royal Society of Chemistry and the Chinese Chemical Society 2018.
PY - 2018
Y1 - 2018
N2 - 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 p-columns, whereas the alternating p-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 p-columns flanked by another bper molecule, bper molecules in the 3: 1 cation radical salt with Mo6O19 2 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 HOMO1 of bper is significantly larger than that of coronene, which is comparable to the intermolecular transfer integrals.
AB - 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 p-columns, whereas the alternating p-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 p-columns flanked by another bper molecule, bper molecules in the 3: 1 cation radical salt with Mo6O19 2 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 HOMO1 of bper is significantly larger than that of coronene, which is comparable to the intermolecular transfer integrals.
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U2 - 10.1039/c8qm00112j
DO - 10.1039/c8qm00112j
M3 - Article
AN - SCOPUS:85060039194
VL - 2
SP - 1165
EP - 1174
JO - Materials Chemistry Frontiers
JF - Materials Chemistry Frontiers
SN - 2052-1537
IS - 6
ER -