Substituent-mediated transformation of polynuclear gold(I)-sulfido complexes—from pentanuclear to octadecanuclear cluster-to-cluster transformation

Polynuclear gold complexes show diverse structures and bonding. An exploration into their transformation represents a challenging area of research. Herein, an unprecedented substituent-mediated transformation from pentagold(I) to octadecagold(I) complexes has been observed. These gold(I)-sulfido complexes with distinct structures have been fully characterized, and the transformation process has been monitored by NMR spectroscopy in solution state. The electron-withdrawing effects of the substituent groups on the diphosphine ligands have given rise to subtle changes in the electron density on the gold(I) center, which has resulted in the structural reorganization of the clusters to maximize Au···Au interactions. This compensates for the loss of electron density at the metal center, leading to different symmetries and nuclearities of gold(I)sulfido complexes with distinctly different photophysical properties. 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 by varying the electronic nature of the substituent on the phosphine ligand.