Suppression of a Structural Phase Transition by an Orientational Disorder of Counteranions in an Organic Conductor, β″-β″-(BEDT-TTF)₂ClC₂H₄SO₃

Akutsu, Hiroki; Uruichi, Mikio; Imajo, Shusaku; Kindo, Koichi; Masuta, Takato; Manabe, Haruhito; Nakazawa, Yasuhiro; Turner, Scott S.

doi:https://doi.org/10.1021/acs.inorgchem.4c02735

Suppression of a Structural Phase Transition by an Orientational Disorder of Counteranions in an Organic Conductor, β″-β″-(BEDT-TTF)₂ClC₂H₄SO₃

Akutsu, Hiroki; Uruichi, Mikio; Imajo, Shusaku et al.

Inorganic Chemistry, 2024, 63(36), 16872-16877

Number of Access:553（2025-12-10 23:42 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/98235

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Title	Suppression of a Structural Phase Transition by an Orientational Disorder of Counteranions in an Organic Conductor, β″-β″-(BEDT-TTF)₂ClC₂H₄SO₃
Creator	NRID 1000080316033 1000080316033 researchmap permalink read0054913 read0054913 Scopus Author ID 7102483241 7102483241 CreatorName Akutsu, Hiroki
	NRID 1000070390680 1000070390680 CreatorName Uruichi, Mikio
	NRID 1000030825352 1000030825352 CreatorName Imajo, Shusaku
	NRID 1000020205058 1000020205058 CreatorName Kindo, Koichi
	CreatorName Masuta, Takato
	CreatorName Manabe, Haruhito
	NRID 1000060222163 1000060222163 researchmap permalink thermo102 thermo102 Scopus Author ID 55556980600 55556980600 CreatorName Nakazawa, Yasuhiro
	CreatorName Turner, Scott S.
Description	Akutsu H., Uruichi M., Imajo S., et al. Suppression of a Structural Phase Transition by an Orientational Disorder of Counteranions in an Organic Conductor, β″-β″-(BEDT-TTF)₂ClC₂H₄SO₃. Inorganic Chemistry 63, 16872 (2024); https://doi.org/10.1021/acs.inorgchem.4c02735.
Abstract	In 2022, we reported that the β″-(BEDT-TTF)₂ClC₂H₄SO₃ salt (1) has a phase transition at 210 K on cooling and 260 K on heating, which was suggested as a nondoped-to-doped transition. During the synthesis of 1, a second salt was coproduced, the structure and properties of which are reported here. The new salt β″-β″-(BEDT-TTF)₂ClC₂H₄SO₃ (2) has the same composition and is isomorphous to 1L, the low-temperature phase of 1. However, the salt shows no phase transition. 1H, the high-temperature phase of 1, displays rotational disorders of the −SO₃- groups. In contrast, the anions in 2 have no rotational disorders but have orientational disorders. Approximately 13% of the anions in 2 have their orientation as opposed to the remaining anions. The geometrically calculated shortest O···O distance is 2.24 Å if neighbor −SO₃- groups are able to rotate freely. This is 1.1 Å shorter than the sum of the van der Waals radii, and therefore, this is too close to allow free rotation. Therefore, it is proposed that 2 has no rotational disorder, which leads to no phase transition as is observed in 1.
Publisher	American Chemical Society
Source Title	Inorganic Chemistry
Volume (Issue)	63(36)
Page	16872-16877
Date of Issued	2024-09-09
Language	English
Handle URL	https://hdl.handle.net/11094/98235
PISSN	00201669
eISSN	1520510X
Relation.isVersionOf	DOI (Publisher Version) https://doi.org/10.1021/acs.inorgchem.4c02735
Access Rights	open access
CopyRight	This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.4c02735.
oaire:version	Accepted Manuscript
Category	学術雑誌論文 Journal Article

Resource Type	journal article
Local Type	Journal Article
DCTERMS.bibliographicCitation	Inorganic Chemistry. 2024, 63(36), p. 16872-16877
DC.title	Suppression of a Structural Phase Transition by an Orientational Disorder of Counteranions in an Organic Conductor, β″-β″-(BEDT-TTF)₂ClC₂H₄SO₃
DC.creator	Akutsu, Hiroki
	Uruichi, Mikio
	Imajo, Shusaku
	Kindo, Koichi
	Masuta, Takato
	Manabe, Haruhito
	Nakazawa, Yasuhiro
	Turner, Scott S.
DC.publisher	American Chemical Society
DC.language' scheme='DCTERMS.RFC1766	English
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2024-09-09
DC.identifier	https://doi.org/10.1021/acs.inorgchem.4c02735
DC.description	Akutsu H., Uruichi M., Imajo S., et al. Suppression of a Structural Phase Transition by an Orientational Disorder of Counteranions in an Organic Conductor, β″-β″-(BEDT-TTF)₂ClC₂H₄SO₃. Inorganic Chemistry 63, 16872 (2024); https://doi.org/10.1021/acs.inorgchem.4c02735.
DCTERMS.abstract	In 2022, we reported that the β″-(BEDT-TTF)₂ClC₂H₄SO₃ salt (1) has a phase transition at 210 K on cooling and 260 K on heating, which was suggested as a nondoped-to-doped transition. During the synthesis of 1, a second salt was coproduced, the structure and properties of which are reported here. The new salt β″-β″-(BEDT-TTF)₂ClC₂H₄SO₃ (2) has the same composition and is isomorphous to 1L, the low-temperature phase of 1. However, the salt shows no phase transition. 1H, the high-temperature phase of 1, displays rotational disorders of the −SO₃- groups. In contrast, the anions in 2 have no rotational disorders but have orientational disorders. Approximately 13% of the anions in 2 have their orientation as opposed to the remaining anions. The geometrically calculated shortest O···O distance is 2.24 Å if neighbor −SO₃- groups are able to rotate freely. This is 1.1 Å shorter than the sum of the van der Waals radii, and therefore, this is too close to allow free rotation. Therefore, it is proposed that 2 has no rotational disorder, which leads to no phase transition as is observed in 1.
DC.rights	This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.4c02735.
DC.format	98235
citation_title	Suppression of a Structural Phase Transition by an Orientational Disorder of Counteranions in an Organic Conductor, β″-β″-(BEDT-TTF)₂ClC₂H₄SO₃
citation_author	Akutsu, Hiroki
	Uruichi, Mikio
	Imajo, Shusaku
	Kindo, Koichi
	Masuta, Takato
	Manabe, Haruhito
	Nakazawa, Yasuhiro
	Turner, Scott S.
citation_publisher	American Chemical Society
citation_language	English
citation_date	2024-09-09
citation_journal_title	Inorganic Chemistry
citation_volume	63
citation_issue	36
citation_firstpage	16872
citation_lastpage	16877
citation_doi	https://doi.org/10.1021/acs.inorgchem.4c02735
citation_public_url	https://hdl.handle.net/11094/98235

Suppression of a Structural Phase Transition by an Orientational Disorder of Counteranions in an Organic Conductor, β″-β″-(BEDT-TTF)₂ClC₂H₄SO₃

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