Article Electrically conductive charge-segregated pseudo-polymorphs comprising highly planar expanded π-electronic cation

Yohei Haketa (Ritsumeikan University) ; Ryoya Nakajima (Ritsumeikan University) ; Yuto Maruyama (Ritsumeikan University) ; Hiroki Tanaka (Ritsumeikan University) ; Wookjin Choi (Kyoto University) ; Shu Seki (Kyoto University) ; Shunsuke Sato (Kitasato University) ; Hitomi Baba (Kitasato University) ; Yoshiki Ishii (Kitasato University) ; Go Watanabe (Kitasato University) ; Kirill Bulgarevich (RIKEN Center for Emergent Matter Science) ; Kazuo Takimiya (RIKEN Center for Emergent Matter Science) ; Kenzo Deguchi (Research Network and Facility Services Division/Materials Fabrication and Analysis Platform/High Magnetic Field Characterization Unit, National Institute for Materials Science) ; Shinobu Ohki SAMURAI ORCID (Research Network and Facility Services Division/Materials Fabrication and Analysis Platform/High Magnetic Field Characterization Unit, National Institute for Materials ScienceROR) ; Kenjiro Hashi SAMURAI ORCID (Center for Basic Research on Materials/Advanced Materials Characterization Field/Solid-State NMR Group, National Institute for Materials ScienceROR) ; Takashi Nakanishi SAMURAI ORCID (Research Center for Materials Nanoarchitectonics (MANA)/Nanomaterials Field/Frontier Molecules Group, National Institute for Materials ScienceROR) ; Yukihide Ishibashi (Ehime University) ; Tsuyoshi Asahi (Ehime University) ; Kazuchika Ohta (Shinshu University) ; Hiromitsu Maeda (Ritsumeikan University)

nakajima_250116c_rev.pdf
Download file (1.76 MB)
Download as zip (1.68 MB)
Collection

Citation
Yohei Haketa, Ryoya Nakajima, Yuto Maruyama, Hiroki Tanaka, Wookjin Choi, Shu Seki, Shunsuke Sato, Hitomi Baba, Yoshiki Ishii, Go Watanabe, Kirill Bulgarevich, Kazuo Takimiya, Kenzo Deguchi, Shinobu Ohki, Kenjiro Hashi, Takashi Nakanishi, Yukihide Ishibashi, Tsuyoshi Asahi, Kazuchika Ohta, Hiromitsu Maeda. Electrically conductive charge-segregated pseudo-polymorphs comprising highly planar expanded π-electronic cation. CHEMICAL SCIENCE. 2025, 16 (12), 4998-5006. https://doi.org/10.1039/D4SC07576E

Description:

(abstract)

An expanded π-electronic cation, benzoporphyrin Au(III) complex, was synthesized as the component of ion pairs in combination with counteranions. In contrast to benzoporphyrin, which has been known for its insolubility in organic solvents, the ion pairs with bulky anions in this study were soluble in common organic solvents. The ion pairs formed charge-segregated assemblies as two pseudo-polymorphs of single-crystal and less-crystalline (LeC) states based on stacking the benzoporphyrin Au(III) complex. XRD, solid-state NMR measurements, and molecular dynamics (MD) simulation revealed that the LeC states were formed by a less-ordered arrangement of constituting ions induced by bulky counteranions. Electric conductive properties were observed in the obtained single-crystal and LeC charge-segregated assemblies.

Rights:

Keyword: charge-segregated assembly, porphyrin Au complexes, ion pairs

Date published: 2025-02-19

Publisher: Royal Society of Chemistry

Journal:

  • CHEMICAL SCIENCE (ISSN: 20416520) vol. 16 issue. 12 p. 4998-5006

Funding:

  • JSPS JP18H01968, JP22H02067, JP23K23335, JP19K05444, JP24K08389, JP20J22745, JP23K17951, JP20H05863
  • JST JPMJSP2101

Manuscript type: Author's version (Accepted manuscript)

MDR DOI: https://doi.org/10.48505/nims.5377

First published URL: https://doi.org/10.1039/D4SC07576E

Related item:

Other identifier(s):

Contact agent:

Updated at: 2025-03-26 17:26:53 +0900

Published on MDR: 2025-03-26 17:26:53 +0900

Filename Size
Filename nakajima_250116c_rev.pdf (Thumbnail)
application/pdf 		Size 1.76 MB Detail