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Non-luminescent, isostructural crystals of [(C 6 H 11 NC) 2 Au](EF 6 )·C 6 H 6 (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, [(C 6 H 11 NC) 2 Au] + , 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 [(C 6 H 11 NC) 2 Au] + ions are isolated from one another. In [(C 6 H 11 NC) 2 Au](BArF 24 ) ((BArF 24 ) − 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 [(C 6 H 11 NC) 2 Au](EF 6 ) (E = As or Sb, but not P) from benzene solution produces colorless, non-emissive crystals of the solvates [(C 6 H 11 NC) 2 Au](EF 6 )·C 6 H 6 . 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 [(C 6 H 11 NC) 2 Au](SbF 6 )·C 6 H 6 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 [(C 6 H 11 NC) 2 Au](SbF 6 ) 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 [(C 6 H 11 NC) 2 Au](AsF 6 )·C 6 H 6 stand in air, they lose benzene and are converted into the yellow, green-luminescent polymorph of [(C 6 H 11 NC) 2 Au](AsF 6 ) 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 [(C 6 H 11 NC) 2 Au](AsF 6 ) are sensitive to benzene vapor and are converted by exposure to benzene vapor into the colorless, blue-luminescent polymorph.
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