RT Journal Article
T1 Cross-conjugated isothianaphthene quinoids: a versatile strategy for controlling electronic structures
A1 Yamamoto, Keitaro
A1 Moles Quintero, Sergio
A1 Jinnai, Seihou
A1 Jeong, Eunjeong
A1 Matsuo, Kyohei
A1 Suzuki, Mitsuharu
A1 Yamada, Hiroko
A1 Casado-Cordón, Juan
A1 Ie, Yutaka
K1 Estructura electrónica
AB The elucidation of new structure–property relationships in π-conjugated molecules bearing quinoidal moieties is of relevance because of their use in organic electronics applications and their traditional assimilation as models of doped conducting polymers. Quinoidal oligothiophenes are ground state electronic hybrids between closed-shell Kekulé quinoidal and open-shell aromatic diradicaloid forms. The prominent contribution of the diradical character in longer oligomers beyond thiophene 4-mers results in a low stability, thereby limiting the ability to tune their properties. Thus, the control of these quinoidal/aromatic contributions is an important prerequisite to develop long quinoidal oligothiophenes. To address this problem, a series of quinoidal pentathiophenes with benzene-annelated isothianaphthene units were designed and successfully synthesized as stable structures. Combined molecular spectroscopies and theoretical modelling indicated that cross-conjugation appears upon the introduction of multiple benzene-annelated units, and that the number and position of the benzene-annelated units have a significant influence on the quinoidal/aromatic/cross-conjugated electronic structures. The newly developed quinoidal pentathiophenes functioned as organic semiconducting materials in transistor and near infrared phototransistor devices. This study demonstrates that modification of the cross-conjugated quinoidal structure is a promising strategy for fine-tuning electronic structures in π-extended quinoidal systems, which could help us to understand unique π-electronic features and to develop novel organic electronic materials.
PB RSC
YR 2022
FD 2022-02-22
LK https://hdl.handle.net/10630/26531
UL https://hdl.handle.net/10630/26531
LA eng
NO Yamamoto, K., Quintero, S. M., Jinnai, S., Jeong, E., Matsuo, K., Suzuki, M., ... & Ie, Y. (2022). Cross-conjugated isothianaphthene quinoids: a versatile strategy for controlling electronic structures. Journal of Materials Chemistry C, 10(11), 4424-4433.
NO This work was supported by JSPS KAKENHI (20H02814, 20K21224, 20H05841, 20KK0123, 19K15505, 20H04639, 20K15352, 21K05213, 20H00379, 20H05833, and 20K15261), CREST (J205101030), NEDO (21500248-0), and “Dynamic Alliance for Open Innovation Bridging Human, Environmental and Materials” from The Ministry of Education, Culture, Sports, Science and Technology, Japan. We are grateful to Prof. Toshihiro Ohnishi for helpful discussion. The authors thank the Spanish Ministry of Science, Innovation and Universities MCIU and MINECO/FEDER of the Spanish Government (project PGC2018-098533-B-100), the Ministry of Science and Technology of the Spanish Government (project RED2018-102626-T) and the Junta de Andalucía, Spain (UMA18FEDERJA057). We also thank the Research Central Services (SCAI) of the University of Málaga.   //   Funding for open access charge: Universidad de Málaga
DS RIUMA. Repositorio Institucional de la Universidad de Málaga
RD 25 ene 2026