Depending upon the crystallization conditions, [Au{C(NHMe)(2)}(2)](AsF6) forms colorless crystals that display a blue or green luminescence. The difference involves the type of solvate molecule that is incorporated into the crystal and the structure of the chains of cations that are formed upon crystallization. The crystallographically determined structures of blue-glowing [Au{C(NHMe)(2)}(2)](AsF6) center dot 0.5(benzene), blue-glowing [Au(C(NHMe)(2)}(2)](AsF6) center dot 0.5(acetone), green-glowing [Au[C(NHMe)(2)}(2)](AsF6) center dot 0.5(chlorobenzene), and blue-glowing, solvate-free [Au[C(NHMe)(2)}(2)](EF6), E = P, As, Sb are reported. All pack with the cations forming extended columns, which may be linear or bent, but all show significant aurophilic interactions. The blue-glowing crystals have ordered stacks of cations with some variation in structural arrangement whereas the green-glowing crystals have disorder in their stacking pattern. Although there is extensive hydrogen bonding between the cations and anions in all structures, in the solvated crystals, the solvate molecules occupy channels but make no hydrogen-bonded contacts. The emission spectra of these new salts taken at 298 and 77 K are reported.