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

Nishimura, Rio; Yamashita, Ken‐ichi

Chemistry – A European Journal, 2025, e202501123

Number of Access:14（2025-08-28 17:32 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/102242

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Title
Effect of Chalcogen Interaction on the Structure of Methine‐Bridged Trichalcogenophenes
Creator
CreatorName
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
CreatorName
Yamashita, Ken‐ichi
Description
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.
Abstract
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.
Publisher
Wiley
Source Title
Chemistry – A European Journal
Page
e202501123
Date of Issued
2025-05-26
Language
English
Handle URL
https://hdl.handle.net/11094/102242
PISSN
09476539
eISSN
15213765
Relation.isIdenticalTo
DOI (Publisher Version)
https://doi.org/10.1002/chem.202501123
Access Rights
open access
CopyRight
This article is licensed under a Creative Commons Attribution 4.0 International License.
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Category
学術雑誌論文 Journal Article