Role of Anions and Mixtures of Anions on the Thermochromism, Vapochromism, and Polymorph Formation of Luminescent Crystals of a Single Cation, [(C6H11NC)2Au]+

Noncoordinating anions, which generally play a subordinate role in coordination chemistry, alter the structure, the luminescence, as well as the thermochromic and vapochromic behaviors of salts of the two-coordinate cation, [(C6H11NC)2Au]+. Thus whereas the yellow polymorphs of [(C6H11NC)2Au]­(PF6) and [(C6H11NC)2Au]­(AsF6) contain single chains of cations and are vapochromic, yellow [(C6H11NC)2Au]­(SbF6) does not form the same polymorph and is not vapochromic but contains two distinct chains of cations connected through aurophilic interactions. Mixed crystals such as [(C6H11NC)2Au]­(PF6)0.50(AsF6)0.50 have been prepared by adding diethyl ether to a dichloromethane solution containing equimolar amounts of [(C6H11NC)2Au]­(PF6) and [(C6H11NC)2Au]­(AsF6). The initial (kinetic) product for the three combinations of anions ((PF6)−/(AsF6)−, (PF6)−/(SbF6)−, and (AsF6)−/(SbF6)−) was a precipitate of fine yellow needles with a green emission, which were gradually transformed at rates that depended on the anions present into colorless crystals with a blue emission. Whereas neither polymorph of [(C6H11NC)2Au]­(PF6) nor [(C6H11NC)2Au]­(SbF6) is thermochromic, the colorless mixed crystal [(C6H11NC)2Au]­(PF6)0.50(SbF6)0.50 is thermochromic and converts from blue-emitting to green-emitting at 87–95 °C. The temperature required to transform a crystal of the type [(C6H11NC)2Au]­(PF6)n(AsF6)1–n from colorless (blue-emitting) to yellow (green-emitting) increases as the fraction of hexafluorophosphate ion in the crystal increases. The yellow crystals of [(C6H11NC)2Au]­(PF6)0.75(AsF6)0.25, [(C6H11NC)2Au]­(PF6)0.50(AsF6)0.50, and [(C6H11NC)2Au]­(PF6)0.25(AsF6)0.75 are vapochromic, whereas the yellow crystals of [(C6H11NC)2Au]­(PF6)0.50(SbF6)0.50 and [(C6H11NC)2Au]­(AsF6)0.50(SbF6)0.50 are not.