Synthesis and Characterization of Silver(I) and Gold(I) Complexes Bearing a Pyrido-annelated N-Heterocyclic Carbene: A Rare Example of a Cocrystal Containing Two Different Gold(I) Complexes

摘要

The cyclohexyl-substituted imidazo[1,5-a]pyridin-2-ium hexafluorophosphate, 2a, has been prepared as precursor for the respective pyrido-annelated N-heterocyclic carbene. [(NHC)(2)Ag]PF6, 3, has been synthesized by the reaction of 2a with AgCl/KOH in dichloromethane (DCM). Unexpectedly, the reaction of 3 with (tht)AuBr yielded both (NHC)AuBr and [(NHC)Au(tht)]PF6 which formed a 1: 1 cocrystal (4a,b). The complexes are aggregated to infinite chains, which are governed by both pi-pi stacking and weak aurophilic interactions. Subsequent oxidation of the co-crystalline material with CsBr3 gave (NHC)AuBr3, 5. All compounds were characterized by NMR spectroscopy, mass spectrometry and elemental analysis. Additionally, compounds 2a and 5 were investigated by electronic spectroscopy: 2a behaves like a typical aromatic compound exhibiting absorption and fluorescence bands attributable to pi-pi* transitions. The Au(III) complex 5 exhibits ligand-centered fluorescence at room temperature and both ligand-centered fluorescence and a weak phosphorescence at 77 K.