Benzo[cd]Perylenyl: A π-Expanded Phenalenyl Radical With Enhanced Aggregation Enthalpy and Stability

Ono, Yuga; Goto, Yuko; Tani, Yosuke; Nakasuji, Kazuhiro; Sato, Kazunobu; Takui, Takeji; Shimizu, Daiki; Matsuda, Kenji; Kubo, Takashi

doi:https://doi.org/10.1002/ajoc.202500300

Benzo[cd]Perylenyl: A π-Expanded Phenalenyl Radical With Enhanced Aggregation Enthalpy and Stability

Ono, Yuga; Goto, Yuko; Tani, Yosuke et al.

Asian Journal of Organic Chemistry, 2025, e202500300

Number of Access:355（2025-09-04 14:41 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/101399

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Title	Benzo[cd]Perylenyl: A π-Expanded Phenalenyl Radical With Enhanced Aggregation Enthalpy and Stability
Creator	CreatorName Ono, Yuga
	CreatorName Goto, Yuko
	NRID 1000000769383 1000000769383 CreatorName Tani, Yosuke
	CreatorName Nakasuji, Kazuhiro
	NRID 1000090264796 1000090264796 CreatorName Sato, Kazunobu
	NRID 1000010117955 1000010117955 CreatorName Takui, Takeji
	NRID 1000010845019 1000010845019 CreatorName Shimizu, Daiki
	NRID 1000080262145 1000080262145 CreatorName Matsuda, Kenji
	NRID 1000060324745 1000060324745 ORCID 0000-0001-6809-7396 0000-0001-6809-7396 researchmap permalink read0076571 read0076571 Scopus Author ID 55576439300 55576439300 CreatorName Kubo, Takashi
Subject	Neutral radical
	Phenalenyl radical
	Polycyclic aromatic hydrocarbon
	Two electron multicenter bonding
	Π-dimer
Description	Ono Y., Goto Y., Tani Y., et al. Benzo[cd]Perylenyl: A π-Expanded Phenalenyl Radical With Enhanced Aggregation Enthalpy and Stability. Asian Journal of Organic Chemistry (2025); https://doi.org/10.1002/ajoc.202500300.
Abstract	We report the synthesis and characterization of a π-expanded neutral PAH radical, benzo[cd]perylenyl (1) derived from the phenalenyl radical (2). Hückel molecular orbital (HMO) analysis reveals a uniformly distributed SOMO that enables effective two-electron 20-center bonding in a π-dimer. ESR measurements of 1 show a long half-life of 63 days in air-saturated toluene at room temperature. Temperature-dependent ESR and absorption spectra as well as DFT calculations confirm the preferential formation of a π-dimer over a σ-dimer with an association energy of approximately −65 kJ mol⁻¹, driven by enhanced dispersion interactions. These findings demonstrate that π-expansion stabilizes organic radicals without bulky substituents while preserving intermolecular interactions offering new prospects for advanced materials in electronics and spintronics.
Publisher	John Wiley and Sons Inc
Source Title	Asian Journal of Organic Chemistry
Page	e202500300
Date of Issued	2025-03-27
Language	English
Handle URL	https://hdl.handle.net/11094/101399
eISSN	21935815
Relation.isIdenticalTo	DOI (Publisher Version) https://doi.org/10.1002/ajoc.202500300
Access Rights	open access
CopyRight	This article is licensed under a Creative Commons Attribution 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
DCMI Type	Text
DCTERMS.bibliographicCitation	Asian Journal of Organic Chemistry. 2025, p. e202500300
DC.title	Benzo[cd]Perylenyl: A π-Expanded Phenalenyl Radical With Enhanced Aggregation Enthalpy and Stability
DC.creator	Ono, Yuga
	Goto, Yuko
	Tani, Yosuke
	Nakasuji, Kazuhiro
	Sato, Kazunobu
	Takui, Takeji
	Shimizu, Daiki
	Matsuda, Kenji
	Kubo, Takashi
DC.publisher	John Wiley and Sons Inc
DC.language' scheme='DCTERMS.RFC1766	English
DC.type' scheme='DCTERMS.DCMIType	Text
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2025-03-27
DC.identifier	https://doi.org/10.1002/ajoc.202500300
DC.subject	Neutral radical
	Phenalenyl radical
	Polycyclic aromatic hydrocarbon
	Two electron multicenter bonding
	Π-dimer
DC.description	Ono Y., Goto Y., Tani Y., et al. Benzo[cd]Perylenyl: A π-Expanded Phenalenyl Radical With Enhanced Aggregation Enthalpy and Stability. Asian Journal of Organic Chemistry (2025); https://doi.org/10.1002/ajoc.202500300.
DCTERMS.abstract	We report the synthesis and characterization of a π-expanded neutral PAH radical, benzo[cd]perylenyl (1) derived from the phenalenyl radical (2). Hückel molecular orbital (HMO) analysis reveals a uniformly distributed SOMO that enables effective two-electron 20-center bonding in a π-dimer. ESR measurements of 1 show a long half-life of 63 days in air-saturated toluene at room temperature. Temperature-dependent ESR and absorption spectra as well as DFT calculations confirm the preferential formation of a π-dimer over a σ-dimer with an association energy of approximately −65 kJ mol⁻¹, driven by enhanced dispersion interactions. These findings demonstrate that π-expansion stabilizes organic radicals without bulky substituents while preserving intermolecular interactions offering new prospects for advanced materials in electronics and spintronics.
DC.rights	This article is licensed under a Creative Commons Attribution 4.0 International License.
DC.format	101399
citation_title	Benzo[cd]Perylenyl: A π-Expanded Phenalenyl Radical With Enhanced Aggregation Enthalpy and Stability
citation_author	Ono, Yuga
	Goto, Yuko
	Tani, Yosuke
	Nakasuji, Kazuhiro
	Sato, Kazunobu
	Takui, Takeji
	Shimizu, Daiki
	Matsuda, Kenji
	Kubo, Takashi
citation_publisher	John Wiley and Sons Inc
citation_language	English
citation_date	2025-03-27
citation_journal_title	Asian Journal of Organic Chemistry
citation_firstpage	e202500300
citation_doi	https://doi.org/10.1002/ajoc.202500300
citation_public_url	https://hdl.handle.net/11094/101399

Benzo[cd]Perylenyl: A π-Expanded Phenalenyl Radical With Enhanced Aggregation Enthalpy and Stability

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