Photophysics of Bis(thiocyanato)gold(I) Complexes: Intriguing Structure−Luminescence Relationships

The electronic structure of bis(thiocyanato)gold(I) complexes is studied both experimentally and theoretically. Temperature-dependent photoluminescence studies for K[Au(SCN)2] reveal two unstructured luminescence bands:  a strong green phosphorescence band (τ77K = 45.4 μs) and a weak blue fluorescence band (τ77K = 24.4 ns) that becomes well-resolved by cooling toward 4 K or by time-resolved measurements, representing a rare case for Au(I) compounds whereby both fluorescence and phosphorescence are observed simultaneously. Quantum mechanical calculations for dimeric models indicate Au−Au covalent bond formation in the T1 lowest triplet excited state (2.62 A; υAu-Au = 180 cm-1), compared to corresponding values of 2.95 A and 84 cm-1, respectively, for the aurophilically bound S0 ground state. Intriguing structure−luminescence relations exist for bis(thiocyanato)gold(I) complexes with different cations such as K+, Rb+, n-Bu4N+, and Cs+ in which the salts with shorter Au···Au nearest-neighbor separations show...

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