The tetrahedral Au complexes [Au(GeCl )L ] (L=PMe (1), PMe Ph (2), PMePh (3), PPh (4)) were synthesized by in situ treatment of the [Au(GeCl )(tht)] complex with three equivalents of the corresponding tertiary phosphine. The crystal structures of complexes 1 and 3 have been determined through X-ray diffraction studies and show [GeCl ] fragments bonded to the corresponding [Au(PR ) ] units through covalent bonds, leading to a tetrahedral coordination environment for gold. Complexes 3 and 4 show dual phosphorescence in the solid state at 77 K and, in the case of complex 4, an interesting room-temperature mechanochromism effect is observed. Correlated MP2, SCS-MP2, SCS-CC2, and ONIOM MP2/UFF calculations suggest the existence of two largely distorted and thermally connected triplet excited states (T and T ) for a model system of complex 4. The AuP moiety can be distorted in two different planes leading to the two triplet excited states T and T , leaving the GeCl unit almost unaltered. The emissions of these phosphorescent Au Ge complexes is mainly ascribed to a metal (gold)-centered ( MC) transition with some contribution from the [GeCl ] fragments.
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