Aggregation-Induced Phosphorescence of a Trans-Bis(iminomethylpyrolato)Platinum Complex Bearing a Polymethylene Vaulted Structure: Chain Length–Dependent Solid-State Emissions

Kawamorita, Soichiro; Huang, Shufang; Yoshida, Atsushi; Suzuki, Shuichi; Naota, Takeshi

doi:https://doi.org/10.1002/chem.202501670

Aggregation-Induced Phosphorescence of a Trans-Bis(iminomethylpyrolato)Platinum Complex Bearing a Polymethylene Vaulted Structure: Chain Length–Dependent Solid-State Emissions

Kawamorita, Soichiro; Huang, Shufang; Yoshida, Atsushi et al.

Chemistry - A European Journal, 2025, 31(45), e01670

アクセス数:186件（2026-02-16 10:17 集計）

固定URL: https://hdl.handle.net/11094/102948

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タイトル	Aggregation-Induced Phosphorescence of a Trans-Bis(iminomethylpyrolato)Platinum Complex Bearing a Polymethylene Vaulted Structure: Chain Length–Dependent Solid-State Emissions
著者	NRID 1000000708472 1000000708472 ORCID 0000-0002-2093-5175 0000-0002-2093-5175 researchmap permalink S.Kawamorita S.Kawamorita Scopus Author ID 25644145600 25644145600 著者名 Kawamorita, Soichiro
	著者名 Huang, Shufang
	著者名 Yoshida, Atsushi
	NRID 1000080433291 1000080433291 ORCID 0000-0001-6294-9084 0000-0001-6294-9084 researchmap permalink read0210228 read0210228 Scopus Author ID 55388296800 55388296800 著者名 Suzuki, Shuichi
	NRID 1000020164113 1000020164113 著者名 Naota, Takeshi
キーワード等	aggregation-induced emission
	minimum energy crossing point
	phosphorescence
	platinum
内容	Kawamorita S., Huang S., Yoshida A., et al. Aggregation-Induced Phosphorescence of a Trans-Bis(iminomethylpyrolato)Platinum Complex Bearing a Polymethylene Vaulted Structure: Chain Length–Dependent Solid-State Emissions. Chemistry - A European Journal 31, e01670 (2025); https://doi.org/10.1002/chem.202501670.
抄録	Aggregation-induced emission (AIE) has recently attracted considerable attention. Although phosphorescent transition-metal complexes exhibit significant potential as aggregation-induced emission luminogens (AIEgens), their exploration and utilization have remained limited, partly due to the insufficient understanding of the underlying mechanisms. Here, we report a new series of platinum(II) complexes, trans-bis(2-iminomethylpyrrolato)platinum derivatives (1a–d), which feature vaulted polymethylene chains of varying lengths (n = 9–12) that bridge over the metal atom. Notably, racemic complexes 1b and 1d (with chain lengths of 10 and 12) exhibit strong yellow emission in the crystalline state (quantum yields of 24% and 33%, respectively), despite showing no emission in solution. X-ray diffraction analysis revealed face-to-face dimer packing in these emissive crystals, suggesting that dimer formation contributes to their enhanced emission. In contrast, complexes with odd-numbered chain lengths (1a and 1c) showed no such emission enhancement. Density functional theory (DFT) calculations revealed that the minimum energy crossing point (MECP) between the excited triplet and ground state lies at significantly higher energy in the dimeric structure than in the monomer, suggesting suppression of nonradiative decay in the crystalline state. This work provides a design strategy for inducing solid-state phosphorescence by controlling the 3D molecular structure to facilitate favorable molecular stacking while suppressing nonradiative decay pathways.
出版者	John Wiley and Sons Inc
収録物名	Chemistry - A European Journal
巻(号)	31(45)
ページ	e01670
刊行年月	2025-07-31
言語	英語
ハンドルURL	https://hdl.handle.net/11094/102948
PISSN	09476539
eISSN	15213765
関連情報 (isIdenticalTo)	DOI (出版社版) https://doi.org/10.1002/chem.202501670
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. 2025, 31(45), p. e01670
DC.title	Aggregation-Induced Phosphorescence of a Trans-Bis(iminomethylpyrolato)Platinum Complex Bearing a Polymethylene Vaulted Structure: Chain Length–Dependent Solid-State Emissions
DC.creator	Kawamorita, Soichiro
	Huang, Shufang
	Yoshida, Atsushi
	Suzuki, Shuichi
	Naota, Takeshi
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	2025-07-31
DC.identifier	https://doi.org/10.1002/chem.202501670
DC.subject	aggregation-induced emission
	minimum energy crossing point
	phosphorescence
	platinum
DC.description	Kawamorita S., Huang S., Yoshida A., et al. Aggregation-Induced Phosphorescence of a Trans-Bis(iminomethylpyrolato)Platinum Complex Bearing a Polymethylene Vaulted Structure: Chain Length–Dependent Solid-State Emissions. Chemistry - A European Journal 31, e01670 (2025); https://doi.org/10.1002/chem.202501670.
DCTERMS.abstract	Aggregation-induced emission (AIE) has recently attracted considerable attention. Although phosphorescent transition-metal complexes exhibit significant potential as aggregation-induced emission luminogens (AIEgens), their exploration and utilization have remained limited, partly due to the insufficient understanding of the underlying mechanisms. Here, we report a new series of platinum(II) complexes, trans-bis(2-iminomethylpyrrolato)platinum derivatives (1a–d), which feature vaulted polymethylene chains of varying lengths (n = 9–12) that bridge over the metal atom. Notably, racemic complexes 1b and 1d (with chain lengths of 10 and 12) exhibit strong yellow emission in the crystalline state (quantum yields of 24% and 33%, respectively), despite showing no emission in solution. X-ray diffraction analysis revealed face-to-face dimer packing in these emissive crystals, suggesting that dimer formation contributes to their enhanced emission. In contrast, complexes with odd-numbered chain lengths (1a and 1c) showed no such emission enhancement. Density functional theory (DFT) calculations revealed that the minimum energy crossing point (MECP) between the excited triplet and ground state lies at significantly higher energy in the dimeric structure than in the monomer, suggesting suppression of nonradiative decay in the crystalline state. This work provides a design strategy for inducing solid-state phosphorescence by controlling the 3D molecular structure to facilitate favorable molecular stacking while suppressing nonradiative decay pathways.
DC.rights	This article is licensed under a Creative Commons Attribution 4.0 International License.
DC.format	102948
citation_title	Aggregation-Induced Phosphorescence of a Trans-Bis(iminomethylpyrolato)Platinum Complex Bearing a Polymethylene Vaulted Structure: Chain Length–Dependent Solid-State Emissions
citation_author	Kawamorita, Soichiro
	Huang, Shufang
	Yoshida, Atsushi
	Suzuki, Shuichi
	Naota, Takeshi
citation_publisher	John Wiley and Sons Inc
citation_language	英語
citation_date	2025-07-31
citation_journal_title	Chemistry - A European Journal
citation_volume	31
citation_issue	45
citation_firstpage	e01670
citation_doi	https://doi.org/10.1002/chem.202501670
citation_public_url	https://hdl.handle.net/11094/102948

Aggregation-Induced Phosphorescence of a Trans-Bis(iminomethylpyrolato)Platinum Complex Bearing a Polymethylene Vaulted Structure: Chain Length–Dependent Solid-State Emissions

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