Redox-Induced Interconversion of Two Au Nanoclusters: the Mechanism and the Structure-Bond Dissociation Activity Correlations.

The interconversion of atomically precise nanoclusters represents an excellent platform to understand the structural correlations of nanomaterials at the atomic level. Herein, density functional theory calculations were performed to elucidate the mechanism of the redox-induced interconversion of [Au(dppp)] and [Au(dppp)Cl] (dppp is short for 1,3-bis(diphenylphosphino)propane) nanoclusters. Reduction is the driving force for the conversion of [Au(dppp)Cl] to [Au(dppp)], while the Au-Au and first Au-Cl bond dissociations occur asynchronously on the two different corner Au atoms to avoid the formation of an electron-deficient Au atom. By contrast, the reduced electron density of [Au(dppp)] by oxidation with O weakens the outmost Au-Au bond therein and facilitates the coordination of the electron-rich chloride(s). The reduction- and oxidation-induced activations, respectively, of Au-Cl and Au-Au bonds and the elucidated principles on the structure-activity correlations might also be generalized to other size conversions upon redox treatment.