Impacts of Fluorination at the Ortho-Position of Carboxy Groups on Tetrakis(biphenyl)ethene-Based Hydrogen-Bonded Framework

Fujii, Takuto; de la Hoz Tomás, Mario; Oketani, Ryusei; Cohen, Boiko; Otake, Ken-ichi; Shiga, Kazuki; Tohnai, Norimitsu; Douhal, Abderrazzak; Hisaki, Ichiro

doi:https://doi.org/10.1002/smll.73406

Impacts of Fluorination at the Ortho-Position of Carboxy Groups on Tetrakis(biphenyl)ethene-Based Hydrogen-Bonded Framework

Fujii, Takuto; de la Hoz Tomás, Mario; Oketani, Ryusei et al.

Small, 2026, e73406

アクセス数:397件（2026-10-22 08:47 集計）

固定URL: https://hdl.handle.net/11094/105123

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タイトル	Impacts of Fluorination at the Ortho-Position of Carboxy Groups on Tetrakis(biphenyl)ethene-Based Hydrogen-Bonded Framework
著者	著者名 Fujii, Takuto
	著者名 de la Hoz Tomás, Mario
	NRID 1000060874956 1000060874956 ORCID 0000-0001-7860-2456 0000-0001-7860-2456 researchmap permalink ryuseioketani ryuseioketani Scopus Author ID 57086955000 57086955000 著者名 Oketani, Ryusei
	著者名 Cohen, Boiko
	NRID 1000020834823 1000020834823 著者名 Otake, Ken-ichi
	著者名 Shiga, Kazuki
	NRID 1000030346184 1000030346184 ORCID 0000-0001-7051-7599 0000-0001-7051-7599 researchmap permalink read0089607 read0089607 Scopus Author ID 6701482198 6701482198 著者名 Tohnai, Norimitsu
	著者名 Douhal, Abderrazzak
	NRID 1000090419466 1000090419466 ORCID 0000-0002-8170-5605 0000-0002-8170-5605 researchmap permalink Ichiro_Hisaki Ichiro_Hisaki Scopus Author ID 12801798700 12801798700 著者名 Hisaki, Ichiro
キーワード等	crystal engineering
	excimer
	fluorescence spectroscopy
	hydrogen-bonded framework
	intramolecular charge transfer
	tetraphenylethene
内容	Fujii T., de la Hoz Tomás M., Oketani R., et al. Impacts of Fluorination at the Ortho-Position of Carboxy Groups on Tetrakis(biphenyl)ethene-Based Hydrogen-Bonded Framework. Small, e73406 (2026); https://doi.org/10.1002/smll.73406.
抄録	Fluorination of building block molecules is one of the effective engineering approaches to modulate molecular assembly in crystalline organic materials. Herein, we constructed a hydrogen-bonded organic framework (HOF) from a tetraphenylethene derivative, 𝗙-𝗖𝗕𝗣𝗘, possessing 3,5-difluoro-4-carboxyphenyl groups. The introduction of fluorine atoms in ortho-positions of the carboxy group makes the conformation of the arms more twisted, resulting in a framework structure different from that formed with the pristine molecule. The resulting HOF, 𝗙-𝗖𝗕𝗣𝗘-𝟭(MeBz), is composed of 𝙨𝙦𝙡-topological hydrogen-bonded network sheets accumulating in a staggered manner without interpenetration; while, the HOF of the pristine compound (𝗖𝗕𝗣𝗘) is composed of three-directionally interpenetrated 𝙨𝙦𝙡-network sheets. Fluorescence spectroscopy and single-crystal microscopy revealed key features of the photophysical behavior of these HOFs. The solvated 𝗙-𝗖𝗕𝗣𝗘 HOF exhibits blue emission due to an intramolecular charge transfer (ICT) event occurring in <15 ps, whereas desolvation induces a red shift, which is attributed to excimer-like species formed in 120 ps and arising from changes in the stacking arrangement of the layers. These findings show the effect of fluorination on the structures and fluorescence behavior of tetraphenylethene-based HOFs, which were thoroughly compared to the pristine 𝗖𝗕𝗣𝗘 molecule and related derivatives.
出版者	John Wiley and Sons Inc
収録物名	Small
ページ	e73406
刊行年月	2026-04-24
言語	英語
ハンドルURL	https://hdl.handle.net/11094/105123
PISSN	16136810
eISSN	16136829
関連情報 (isIdenticalTo)	DOI (出版社版) https://doi.org/10.1002/smll.73406
アクセス権	open access
権利情報	This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 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	Small. 2026, p. e73406
DC.title	Impacts of Fluorination at the Ortho-Position of Carboxy Groups on Tetrakis(biphenyl)ethene-Based Hydrogen-Bonded Framework
DC.creator	Fujii, Takuto
	de la Hoz Tomás, Mario
	Oketani, Ryusei
	Cohen, Boiko
	Otake, Ken-ichi
	Shiga, Kazuki
	Tohnai, Norimitsu
	Douhal, Abderrazzak
	Hisaki, Ichiro
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	2026-04-24
DC.identifier	https://doi.org/10.1002/smll.73406
DC.subject	crystal engineering
	excimer
	fluorescence spectroscopy
	hydrogen-bonded framework
	intramolecular charge transfer
	tetraphenylethene
DC.description	Fujii T., de la Hoz Tomás M., Oketani R., et al. Impacts of Fluorination at the Ortho-Position of Carboxy Groups on Tetrakis(biphenyl)ethene-Based Hydrogen-Bonded Framework. Small, e73406 (2026); https://doi.org/10.1002/smll.73406.
DCTERMS.abstract	Fluorination of building block molecules is one of the effective engineering approaches to modulate molecular assembly in crystalline organic materials. Herein, we constructed a hydrogen-bonded organic framework (HOF) from a tetraphenylethene derivative, 𝗙-𝗖𝗕𝗣𝗘, possessing 3,5-difluoro-4-carboxyphenyl groups. The introduction of fluorine atoms in ortho-positions of the carboxy group makes the conformation of the arms more twisted, resulting in a framework structure different from that formed with the pristine molecule. The resulting HOF, 𝗙-𝗖𝗕𝗣𝗘-𝟭(MeBz), is composed of 𝙨𝙦𝙡-topological hydrogen-bonded network sheets accumulating in a staggered manner without interpenetration; while, the HOF of the pristine compound (𝗖𝗕𝗣𝗘) is composed of three-directionally interpenetrated 𝙨𝙦𝙡-network sheets. Fluorescence spectroscopy and single-crystal microscopy revealed key features of the photophysical behavior of these HOFs. The solvated 𝗙-𝗖𝗕𝗣𝗘 HOF exhibits blue emission due to an intramolecular charge transfer (ICT) event occurring in <15 ps, whereas desolvation induces a red shift, which is attributed to excimer-like species formed in 120 ps and arising from changes in the stacking arrangement of the layers. These findings show the effect of fluorination on the structures and fluorescence behavior of tetraphenylethene-based HOFs, which were thoroughly compared to the pristine 𝗖𝗕𝗣𝗘 molecule and related derivatives.
DC.rights	This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
DC.format	105123
citation_title	Impacts of Fluorination at the Ortho-Position of Carboxy Groups on Tetrakis(biphenyl)ethene-Based Hydrogen-Bonded Framework
citation_author	Fujii, Takuto
	de la Hoz Tomás, Mario
	Oketani, Ryusei
	Cohen, Boiko
	Otake, Ken-ichi
	Shiga, Kazuki
	Tohnai, Norimitsu
	Douhal, Abderrazzak
	Hisaki, Ichiro
citation_publisher	John Wiley and Sons Inc
citation_language	英語
citation_date	2026-04-24
citation_journal_title	Small
citation_firstpage	e73406
citation_doi	https://doi.org/10.1002/smll.73406
citation_public_url	https://hdl.handle.net/11094/105123

Impacts of Fluorination at the Ortho-Position of Carboxy Groups on Tetrakis(biphenyl)ethene-Based Hydrogen-Bonded Framework

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