American Chemical Society
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Linear Gold(I) Halide Complexes with a Diamidocarbene Ligand: Synthesis, Reactivity, and Phosphorescence

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journal contribution
posted on 2023-11-20, 20:11 authored by Charlotte Riley, Nguyen Le Phuoc, Mikko Linnolahti, Alexander S. Romanov
A series of halide and pseudohalide gold complexes (DAC)­Au­(I)­X (DAC = N,N′-diamidocarbene; X = Cl, Br, I, and SCN) were prepared in high yields. All complexes possess linear geometry around the gold atom with no aurophilic interactions between neighboring molecules. Reactivity studies for (DAC)­Au­(I)­Cl revealed that the diamido backbone of the carbene ligand is vulnerable to nucleophilic attack by a strong base, potassium tert-butoxide, resulting in cleavage of the carbene backbone and formation of a neutral trigold cluster. Halide and pseudohalide complexes are bright phosphorescent emitters in the solid state, exhibiting photoluminescence quantum yields up to unity. Phosphorescence occurs in the range 480–520 nm with lifetimes as short as 1 μs, resulting in fast radiative rates up to 9.4 × 105 s–1 which is on par with the most efficient heavy metal emitters. Photophysical properties are explained by the intrinsic π-accepting nature of the DAC carbene and are supported by TDDFT calculations.