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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 interact