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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:

• https://creativecommons.org/licenses/by-nc/3.0/legalcode
  

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

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

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