Noncovalent Synergy: Aurophilicity and Aryl Stacking in Bis(gold(I)aryl)-dmpm Complexes.

Bis(dimethylphosphino)methane (dmpm) was used as a ligand to synthesize four semi-supported dinuclear gold(I) complexes, dmpm(AuR) 2 (R = Cl, C 6 H 5 , C 6 Cl 5 , and C 6 F 5 ), which were studied concerning the synergistic effects of two weak noncovalent interactions: aurophilic and aryl-aryl stacking interactions. The chloro-substituted complex was synthesized by the ligand substitution of (tht)AuCl with dmpm and further functionalized by the reaction with PhMgBr or in situ- generated C 6 Cl 5 Li to afford the phenyl- and pentachlorophenyl-substituted compounds, respectively. The pentafluorophenyl-substituted gold complex was generated by the ligand substitution of (tht)Au(C 6 F 5 ) with dmpm. All complexes were characterized by multinuclear NMR spectroscopy, CHN analyses, and X-ray diffraction experiments. Additionally, the basic photoluminescence properties of dmpm(AuCl) 2 , dmpm(AuC 6 Cl 5 ) 2 , and dmpm(AuC 6 F 5 ) 2 were examined. The aggregation behavior of dmpm(AuC 6 F 5 ) 2 was further investigated by variable-temperature diffusion-ordered NMR spectroscopy experiments.