Crystallographic and luminescence studies on salts of the two-coordinate carbene cation, [Au{C(NHCH3)(NHCH2CH2OH)}2]+, demonstrate the ability of the cation to exist in three different states of aggregation. In colorless, non-luminescent [Au{C(NHCH3)(NHCH2CH2OH)}2]Cl the cation crystallizes as a monomer with the nearest gold(I) center 6.7890(11) Å away. Colorless, luminescent [Au{C(NHCH3)(NHCH2CH2OH)}2]AsF6 forms dimers with an Au⋯Au separation of 3.1288(4) Å. These dimers form weakly associated extended chains of cations with additional Au⋯Au separations of 3.6625(5) Å. [Au{C(NHCH3)(NHCH2CH2OH)}2]PF6 is isostructural. Yellow, luminescent [Au{C(NHCH3)(NHCH2CH2OH)}2]3(AsF6)2Cl·0.5(H2O)2 and [Au{C(NHCH3)(NHCH2CH2OH)}2]3(PF6)2Cl·0.5(H2O)2 form trimers that further aggregate into extended chains with rather short Au⋯Au separations of 3.1301(14) Å, 3.1569(14) Å and 3.1415(14) Å. Absorption, emission and excitation spectra are reported for these salts. The excitation and emission results from the interactions between the gold centers and involves transitions between the filled dz2 band and the empty pz bands with the z axis pointing along the chain of cations.
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