Multi-state Photoswitching in Thienoquinoid-Based Fluorescent Trithiophenes

Nishimura, Rio; Hecht, Stefan; Saito, Shohei; Yamashita, Ken ichi

doi:https://doi.org/10.1002/chem.71423

Multi-state Photoswitching in Thienoquinoid-Based Fluorescent Trithiophenes

Nishimura, Rio; Hecht, Stefan; Saito, Shohei et al.

Chemistry - A European Journal, 2026

アクセス数:13件（2026-08-12 12:30 集計）

固定URL: https://hdl.handle.net/11094/106011

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タイトル	Multi-state Photoswitching in Thienoquinoid-Based Fluorescent Trithiophenes
著者	著者名 Nishimura, Rio
	著者名 Hecht, Stefan
	NRID 1000030580071 1000030580071 ORCID 0000-0003-1863-9956 0000-0003-1863-9956 researchmap permalink read0156671 read0156671 Scopus Author ID 9270732400 9270732400 著者名 Saito, Shohei
	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
キーワード等	conjugation
	fluorescence
	geometrical isomer
	photoisomerization
	thienoquinoid
内容	Nishimura R., Hecht S., Saito S., et al. Multi-state Photoswitching in Thienoquinoid-Based Fluorescent Trithiophenes. Chemistry - A European Journal , (2026); https://doi.org/10.1002/chem.71423.
抄録	Achieving multi-site photoisomerization within a single π-conjugated scaffold while retaining luminescent functionality remains a formidable challenge, as electronic coupling between isomerizable units typically promotes intramolecular energy transfer that suppresses sequential switching, and the additional nonradiative pathways inherent to multiple isomerizable bonds further impede emissive behavior. Herein, we report a methine-bridged trithiophene bearing 2,6-dichlorophenyl substituents, in which two C═C double bonds embedded in a thienoquinoid framework undergo photoisomerization to afford three interconvertible geometrical isomers (ZZ, EZ, and EE). The steric constraint imposed by the ortho-chloro substituents suppresses nonradiative torsional relaxation, yielding a fluorescence quantum yield of 0.40 for the ZZ-isomer in cyclohexane, which decreases upon photoisomerization to the EZ- and EE-isomers—a significant enhancement over the corresponding derivative lacking ortho-substituents on the aryl groups, accompanied by a markedly reduced Stokes shift. The photostationary state composition varies systematically with the irradiation wavelength, primarily reflecting differences in the molar absorption coefficients of the three isomers, thereby enabling wavelength-selective multi-state control over isomer distributions inaccessible under thermodynamic equilibrium. Fluorescence lifetime measurements revealed isomer-dependent excited-state lifetimes, confirming that molecular geometry governs the photophysical properties within this conjugated framework. This study establishes a molecular design strategy for luminescent multi-state photoswitches applicable to multi-level optical information processing.
出版者	John Wiley and Sons Inc
収録物名	Chemistry - A European Journal
刊行年月	2026-07-17
言語	英語
ハンドルURL	https://hdl.handle.net/11094/106011
PISSN	09476539
eISSN	15213765
関連情報 (isIdenticalTo)	DOI (出版社版) https://doi.org/10.1002/chem.71423
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

資源タイプ	学術雑誌論文
ローカル資源タイプ	学術雑誌論文
DCMI資源タイプ	text
DCTERMS.bibliographicCitation	Chemistry - A European Journal. 2026
DC.title	Multi-state Photoswitching in Thienoquinoid-Based Fluorescent Trithiophenes
DC.creator	Nishimura, Rio
	Hecht, Stefan
	Saito, Shohei
	Yamashita, Ken ichi
DC.publisher	John Wiley and Sons Inc
DC.language' scheme='DCTERMS.RFC1766	英語
DC.type' scheme='DCTERMS.DCMIType	text
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2026-07-17
DC.identifier	https://doi.org/10.1002/chem.71423
DC.subject	conjugation
	fluorescence
	geometrical isomer
	photoisomerization
	thienoquinoid
DC.description	Nishimura R., Hecht S., Saito S., et al. Multi-state Photoswitching in Thienoquinoid-Based Fluorescent Trithiophenes. Chemistry - A European Journal , (2026); https://doi.org/10.1002/chem.71423.
DCTERMS.abstract	Achieving multi-site photoisomerization within a single π-conjugated scaffold while retaining luminescent functionality remains a formidable challenge, as electronic coupling between isomerizable units typically promotes intramolecular energy transfer that suppresses sequential switching, and the additional nonradiative pathways inherent to multiple isomerizable bonds further impede emissive behavior. Herein, we report a methine-bridged trithiophene bearing 2,6-dichlorophenyl substituents, in which two C═C double bonds embedded in a thienoquinoid framework undergo photoisomerization to afford three interconvertible geometrical isomers (ZZ, EZ, and EE). The steric constraint imposed by the ortho-chloro substituents suppresses nonradiative torsional relaxation, yielding a fluorescence quantum yield of 0.40 for the ZZ-isomer in cyclohexane, which decreases upon photoisomerization to the EZ- and EE-isomers—a significant enhancement over the corresponding derivative lacking ortho-substituents on the aryl groups, accompanied by a markedly reduced Stokes shift. The photostationary state composition varies systematically with the irradiation wavelength, primarily reflecting differences in the molar absorption coefficients of the three isomers, thereby enabling wavelength-selective multi-state control over isomer distributions inaccessible under thermodynamic equilibrium. Fluorescence lifetime measurements revealed isomer-dependent excited-state lifetimes, confirming that molecular geometry governs the photophysical properties within this conjugated framework. This study establishes a molecular design strategy for luminescent multi-state photoswitches applicable to multi-level optical information processing.
DC.rights	This article is licensed under a Creative Commons Attribution 4.0 International License.
DC.format	106011
citation_title	Multi-state Photoswitching in Thienoquinoid-Based Fluorescent Trithiophenes
citation_author	Nishimura, Rio
	Hecht, Stefan
	Saito, Shohei
	Yamashita, Ken ichi
citation_publisher	John Wiley and Sons Inc
citation_language	英語
citation_date	2026-07-17
citation_journal_title	Chemistry - A European Journal
citation_doi	https://doi.org/10.1002/chem.71423
citation_public_url	https://hdl.handle.net/11094/106011

Multi-state Photoswitching in Thienoquinoid-Based Fluorescent Trithiophenes

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