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

• Published in: Inorganic chemistry 2022-07, Vol.61 (29), p.11325-11334
• Main Authors: Müller, Felix, Ertl, Martin, Neumann, Beate, Stammler, Hans-Georg, Mix, Andreas, Monkowius, Uwe, Mitzel, Norbert W.
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.2c01442

Bis­(dimethylphosphino)­methane (dmpm) was used as a ligand to synthesize four semi-supported dinuclear gold­(I) complexes, dmpm­(AuR)2 (R = Cl, C6H5, C6Cl5, and C6F5), 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 C6Cl5Li to afford the phenyl- and pentachlorophenyl-substituted compounds, respectively. The pentafluorophenyl-substituted gold complex was generated by the ligand substitution of (tht)­Au­(C6F5) 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(AuC6Cl5)2, and dmpm­(AuC6F5)2 were examined. The aggregation behavior of dmpm­(AuC6F5)2 was further investigated by variable-temperature diffusion-ordered NMR spectroscopy experiments.