Dataset Information

Liquid Crystals Comprising ?-Electronic Ions from Porphyrin-AuIII Complexes.

ABSTRACT: Porphyrin-AuIII complexes were found to act as ?-electronic cations, which can combine with various counteranions, including ?-electronic anions. Single-crystal X-ray analyses revealed the formation of assemblies with contributions of charge-by-charge and charge-segregated assemblies, depending on the geometry and electronic state of the counteranions. Porphyrin-AuIII complexes possessing aliphatic alkyl chains formed dimension-controlled ion-pairing assemblies as thermotropic liquid crystals, whose ionic components were highly organized by ?-? stacking and electrostatic interactions.

SUBMITTER: Haketa Y

PROVIDER: S-EPMC6463747 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature

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Liquid Crystals Comprising π-Electronic Ions from Porphyrin-AuIII Complexes.

Haketa Yohei Y Bando Yuya Y Sasano Yoshifumi Y Tanaka Hiroki H Yasuda Nobuhiro N Hisaki Ichiro I Maeda Hiromitsu H

iScience 20190401

Porphyrin-AuIII complexes were found to act as π-electronic cations, which can combine with various counteranions, including π-electronic anions. Single-crystal X-ray analyses revealed the formation of assemblies with contributions of charge-by-charge and charge-segregated assemblies, depending on the geometry and electronic state of the counteranions. Porphyrin-AuIII complexes possessing aliphatic alkyl chains formed dimension-controlled ion-pairing assemblies as thermotro ...[more]

PMID: 30981960

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Project description:Non-luminescent, isostructural crystals of [(C6H11NC)2Au](EF6)·C6H6 (E = As, Sb) lose benzene upon standing in air to produce green luminescent (E = As) or blue luminescent (E = Sb) powders. Previous studies have shown that the two-coordinate cation, [(C6H11NC)2Au]+, self-associates to form luminescent crystals that contain linear or nearly linear chains of cations and display unusual polymorphic, vapochromic, and/or thermochromic properties. Here, we report the formation of non-luminescent crystalline salts in which individual [(C6H11NC)2Au]+ ions are isolated from one another. In [(C6H11NC)2Au](BArF24) ((BArF24)- is tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) each cation is surrounded by two anions that prohibit any close approach of the gold ions. Crystallization of [(C6H11NC)2Au](EF6) (E = As or Sb, but not P) from benzene solution produces colorless, non-emissive crystals of the solvates [(C6H11NC)2Au](EF6)·C6H6. These two solvates are isostructural and contain columns in which cations and benzene molecules alternate. With the benzene molecules separating the cations, the shortest distances between gold ions are 6.936(2) Å for E = As and 6.9717(19) Å for E = Sb. Upon removal from the mother liquor, these crystals crack due to the loss of benzene from the crystal and form luminescent powders. Crystals of [(C6H11NC)2Au](SbF6)·C6H6 that powder out form a pale yellow powder with a blue luminescence with emission spectra and powder X-ray diffraction data that show that the previously characterized [(C6H11NC)2Au](SbF6) is formed. In the process, the distances between the gold(i) ions decrease to ∼3 Å and half of the cyclohexyl groups move from an axial orientation to an equatorial one. Remarkably, when crystals of [(C6H11NC)2Au](AsF6)·C6H6 stand in air, they lose benzene and are converted into the yellow, green-luminescent polymorph of [(C6H11NC)2Au](AsF6) rather than the colorless, blue-luminescent polymorph. Paradoxically, the yellow, green-luminescent powder that forms as well as authentic crystals of the yellow, green-luminescent polymorph of [(C6H11NC)2Au](AsF6) are sensitive to benzene vapor and are converted by exposure to benzene vapor into the colorless, blue-luminescent polymorph.

Dataset Information

Liquid Crystals Comprising ?-Electronic Ions from Porphyrin-AuIII Complexes.

Publications

Liquid Crystals Comprising π-Electronic Ions from Porphyrin-Au<sup>III</sup> Complexes.

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