Effect of Chalcogen Interaction on the Structure of Methine‐Bridged Trichalcogenophenes

Nishimura, Rio; Yamashita, Ken‐ichi

Chemistry – A European Journal, 2025, e202501123

アクセス数:13件（2025-08-28 10:55 集計）

固定URL: https://hdl.handle.net/11094/102242

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タイトル
Effect of Chalcogen Interaction on the Structure of Methine‐Bridged Trichalcogenophenes
著者
著者名
Nishimura, Rio
NRID
1000040468145 1000040468145
ORCID
0000-0001-7270-1234 0000-0001-7270-1234
researchmap permalink
ken1-yamashi ken1-yamashi
Scopus Author ID
35792834600 35792834600
著者名
Yamashita, Ken‐ichi
内容
Nishimura Rio, Yamashita Ken‐ichi. Effect of Chalcogen Interaction on the Structure of Methine‐Bridged Trichalcogenophenes. Chemistry – A European Journal (2025); https://doi.org/10.1002/chem.202501123.
抄録
Polythienylenemethylidenes (PTMs) are promising conjugated polymers for organic electronics owing to their narrow bandgaps and extended π-conjugation. However, their stereochemistry remains unexplored. In this study, methine-bridged trithiophene and trifuran analogs were synthesized to investigate stereochemistry and chalcogen bonding effects. The compounds were obtained as mixtures of ZZ, EZ(= ZE), and EE geometric isomers, established through detailed NMR analyses. At thermal equilibrium, the ZZ isomer predominated in trithiophene (ZZ:(EZ + ZE):EE = 58:35:6), whereas trifuran showed a near-statistical distribution. X-ray crystallography revealed intramolecular S···S chalcogen bonding in trithiophene with S···S distances (≈3.04 Å) shorter than van der Waals radii and C–S···S angles of 171°. Comprehensive conformer searches and DFT calculations not only validated the higher stability of the ZZ isomer in trithiophene but also provided calculated isomer distributions that closely matched the experimental values. Multi-faceted computational analysis (electron localization function (ELF), noncovalent interaction (NCI), quantum theory of atoms in molecules (QTAIM), and natural bond orbital (NBO)) confirmed the presence of these chalcogen-centered interactions and quantified their strength through lone pair (LP)(S)→σ*(S–C) donor-acceptor orbital interactions. Trithiophene exhibited a unique dual-chalcogen bonding mode in the ZZ configuration. These findings elucidate the role of chalcogen bonding in stabilizing ZZ-trithiophenes and contribute to designing PTMs with controlled stereochemistry for organic electronics applications.
出版者
Wiley
収録物名
Chemistry – A European Journal
ページ
e202501123
刊行年月
2025-05-26
言語
英語
ハンドルURL
https://hdl.handle.net/11094/102242
PISSN
09476539
eISSN
15213765
関連情報 (isIdenticalTo)
DOI (出版社版)
https://doi.org/10.1002/chem.202501123
アクセス権
open access
権利情報
This article is licensed under a Creative Commons Attribution 4.0 International License.
出版タイプ
Version of Record
カテゴリ
学術雑誌論文 Journal Article