A series of polynuclear gold(I) sulfido complexes has been synthesized and characterized. A rather small variation in the conformation of the bis(diphenylphosphino)amine or 1,3-bis(diphenylphosphino)benzene ligands has led to distinct differences in the identity of the polynuclear gold(I) sulfido complexes formed. For the bis(diphenylphosphino)amine ligands, a mixture of both the dodecanuclear and decanuclear gold(I) complexes was isolated for the first time. Moreover, unprecedented concentration-dependent reversible cluster-to-cluster transformation between a dodecanuclear gold(I) sulfido complex (LMe-Au12) and a hexanuclear gold(I) sulfido complex (LMe-Au6) has been observed.1 For the 1,3-bis(diphenylphosphino)benzene ligands, a novel substituent-mediated transformation from pentagold(I) to octadecagold(I) complexes has been observed. It was found that the electron-withdrawing substituent on the 1,3-bis(diphenylphosphino)benzene ligand played a key role in regulating the cluster transformation process. For instance, the Au5clusters with electron-withdrawing substituents such as -F and -CN could transform to Au18clusters in solution.2 These studies demonstrate that a precise tuning of the steric effect and electronic nature of the substituent of the phosphine ligand can play a critical role in the regulation of the structure of gold(I) sulfido complexes. Our findings offer a simple and effective cluster-to-cluster transformation strategy for the development of novel luminescent gold(I)-sulfido clusters with controlled structures.

Concentration- and Substituent-Mediated Structural Transformation of Polynuclear Gold(I) Sulfido Complexes

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