Single Crystalline, Non-Stoichiometric Hydrogen-Bonded Organic Frameworks Showing Versatile Fluorescence Depending on Composition Ratios and Distributions

Hashimoto, Taito; Hoz Tomás, Mario de la; Oketani, Ryusei; Cohen, Boiko; Naruoka, Miki; Tohnai, Norimitsu; Douhal, Abderrazzak; Hisaki, Ichiro

doi:https://doi.org/10.1002/anie.202419992

Single Crystalline, Non-Stoichiometric Hydrogen-Bonded Organic Frameworks Showing Versatile Fluorescence Depending on Composition Ratios and Distributions

Hashimoto, Taito; Hoz Tomás, Mario de la; Oketani, Ryusei et al.

Angewandte Chemie - International Edition, 2024, e202419992

Number of Access:809（2025-08-01 13:24 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/100189

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Title	Single Crystalline, Non-Stoichiometric Hydrogen-Bonded Organic Frameworks Showing Versatile Fluorescence Depending on Composition Ratios and Distributions
Creator	ORCID 0009-0000-0288-4768 0009-0000-0288-4768 CreatorName Hashimoto, Taito
	ORCID 0000-0002-8580-1004 0000-0002-8580-1004 CreatorName Hoz Tomás, Mario de la
	NRID 1000060874956 1000060874956 ORCID 0000-0001-7860-2456 0000-0001-7860-2456 researchmap permalink ryuseioketani ryuseioketani Scopus Author ID 57086955000 57086955000 CreatorName Oketani, Ryusei
	ORCID 0000-0002-5400-4678 0000-0002-5400-4678 CreatorName Cohen, Boiko
	CreatorName Naruoka, Miki
	NRID 1000030346184 1000030346184 ORCID 0000-0001-7051-7599 0000-0001-7051-7599 researchmap permalink read0089607 read0089607 Scopus Author ID 6701482198 6701482198 CreatorName Tohnai, Norimitsu
	ORCID 0000-0003-2247-7566 0000-0003-2247-7566 CreatorName 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 CreatorName Hisaki, Ichiro
Subject	co-crystal
	fluorescence microscopy
	hydrogen-bonded organic framework
	multicolor emission
	Nonstoichiometric crystal
Description	Hashimoto T., Hoz Tomás M.d.l., Oketani R., et al. Single Crystalline, Non-Stoichiometric Hydrogen-Bonded Organic Frameworks Showing Versatile Fluorescence Depending on Composition Ratios and Distributions. Angewandte Chemie - International Edition , (2024); https://doi.org/10.1002/anie.202419992.
Abstract	Hydrogen-bonded organic frameworks (HOFs) composed of multicomponent molecules in a non-stoichiometric composition have drawn great interest due to their tunable properties. However, the photobehavior of the single crystals of such mixed HOFs has not been explored. Here, we report on the synthesis, characterization and photobehavior of single crystalline non-stoichiometric HOFs (NS-HOFs). NS-HOFs (BTNT-1) with various composition ratios were successfully obtained as single crystals from two analogue tetratopic carboxylic acids, possessing naphthalene and benzothiadiazole cores (NTTA and BTTA, respectively). The heterogeneous distribution of the components was thoroughly confirmed by time-resolved fluorescence microscopy and local crystallographic analysis using focused synchrotron X-ray radiation. The versatile fluorescence of BTNT-1 behavior depends on the composition ratio and distribution of the component in the single crystals. We observed not only fluorescence bands with various colors such as purple, blue, green and white, depending on the composition ratios, but also different emission bands from a single crystal. We provide details on their emission lifetimes following the composition, emission color and targeted region on the crystal. This work is the first example of single crystal studies applied to organic porous co-crystals and demonstrates unique and versatile optical properties of carboxylic acid-based NS-HOFs. The results provide a concept of creating functional mixed porous materials capable of different and tunable optical properties.
Publisher	John Wiley and Sons Inc
Source Title	Angewandte Chemie - International Edition
Page	e202419992
Date of Issued	2024-12-12
Language	English
Handle URL	https://hdl.handle.net/11094/100189
PISSN	14337851
eISSN	15213773
Relation.isIdenticalTo	DOI (Publisher Version) https://doi.org/10.1002/anie.202419992
Access Rights	open access
CopyRight	This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
oaire:version	Version of Record
Category	学術雑誌論文 Journal Article

Resource Type	journal article
Local Type	Journal Article
DCTERMS.bibliographicCitation	Angewandte Chemie - International Edition. 2024, p. e202419992
DC.title	Single Crystalline, Non-Stoichiometric Hydrogen-Bonded Organic Frameworks Showing Versatile Fluorescence Depending on Composition Ratios and Distributions
DC.creator	Hashimoto, Taito
	Hoz Tomás, Mario de la
	Oketani, Ryusei
	Cohen, Boiko
	Naruoka, Miki
	Tohnai, Norimitsu
	Douhal, Abderrazzak
	Hisaki, Ichiro
DC.publisher	John Wiley and Sons Inc
DC.language' scheme='DCTERMS.RFC1766	English
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2024-12-12
DC.identifier	https://doi.org/10.1002/anie.202419992
DC.subject	co-crystal
	fluorescence microscopy
	hydrogen-bonded organic framework
	multicolor emission
	Nonstoichiometric crystal
DC.description	Hashimoto T., Hoz Tomás M.d.l., Oketani R., et al. Single Crystalline, Non-Stoichiometric Hydrogen-Bonded Organic Frameworks Showing Versatile Fluorescence Depending on Composition Ratios and Distributions. Angewandte Chemie - International Edition , (2024); https://doi.org/10.1002/anie.202419992.
DCTERMS.abstract	Hydrogen-bonded organic frameworks (HOFs) composed of multicomponent molecules in a non-stoichiometric composition have drawn great interest due to their tunable properties. However, the photobehavior of the single crystals of such mixed HOFs has not been explored. Here, we report on the synthesis, characterization and photobehavior of single crystalline non-stoichiometric HOFs (NS-HOFs). NS-HOFs (BTNT-1) with various composition ratios were successfully obtained as single crystals from two analogue tetratopic carboxylic acids, possessing naphthalene and benzothiadiazole cores (NTTA and BTTA, respectively). The heterogeneous distribution of the components was thoroughly confirmed by time-resolved fluorescence microscopy and local crystallographic analysis using focused synchrotron X-ray radiation. The versatile fluorescence of BTNT-1 behavior depends on the composition ratio and distribution of the component in the single crystals. We observed not only fluorescence bands with various colors such as purple, blue, green and white, depending on the composition ratios, but also different emission bands from a single crystal. We provide details on their emission lifetimes following the composition, emission color and targeted region on the crystal. This work is the first example of single crystal studies applied to organic porous co-crystals and demonstrates unique and versatile optical properties of carboxylic acid-based NS-HOFs. The results provide a concept of creating functional mixed porous materials capable of different and tunable optical properties.
DC.rights	This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
DC.format	100189
citation_title	Single Crystalline, Non-Stoichiometric Hydrogen-Bonded Organic Frameworks Showing Versatile Fluorescence Depending on Composition Ratios and Distributions
citation_author	Hashimoto, Taito
	Hoz Tomás, Mario de la
	Oketani, Ryusei
	Cohen, Boiko
	Naruoka, Miki
	Tohnai, Norimitsu
	Douhal, Abderrazzak
	Hisaki, Ichiro
citation_publisher	John Wiley and Sons Inc
citation_language	English
citation_date	2024-12-12
citation_journal_title	Angewandte Chemie - International Edition
citation_firstpage	e202419992
citation_doi	https://doi.org/10.1002/anie.202419992
citation_public_url	https://hdl.handle.net/11094/100189

Single Crystalline, Non-Stoichiometric Hydrogen-Bonded Organic Frameworks Showing Versatile Fluorescence Depending on Composition Ratios and Distributions

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