Nanocluster Transformation Induced by SbF6-Anions toward Boosting Photochemical Activities

The interactions between SbF6- and metal nanoclusters are of significance for customizing clusters from both structure and property aspects; however, the whole-segment monitoring of this customization remains challenging. In this work, by controlling the amount of introduced SbF6- anions, the step-by-step nanocluster evolutions from [Pt1Ag28(S-Adm)18(PPh3)4]Cl2 (Pt1Ag28-Cl) to [Pt1Ag28(S-Adm)18(PPh3)4](SbF6)2 (Pt1Ag28-SbF6) and then to [Pt1Ag30Cl1(S-Adm)18(PPh3)3](SbF6)3 (Pt1Ag30-SbF6) have been mapped out with X-ray crystallography, with which atomic-level SbF6- counterion effects in reconstructing and rearranging nanoclusters are determined. The structure-dependent optical properties, including optical absorption, photoluminescence, and electrochemiluminescence (ECL), of these nanoclusters are then explored. Notably, the Pt1Ag30-SbF6 nanocluster was ultrabright with a high phosphorescence quantum yield of 85% in N2-purged solutions, while Pt1Ag28 nanoclusters were fluorescent with weaker emission intensities. Furthermore, Pt1Ag30-SbF6 displayed superior ECL efficiency over Pt1Ag28-SbF6, which was rationalized by its increased effectively exposed reactive facets. Both Pt1Ag30-SbF6 and Pt1Ag28-SbF6 demonstrated unprecedented high absolute ECL quantum efficiencies at sub-micromolar concentrations. This work is of great significance for revealing the SbF6- counterion effects on the control of both structures and luminescent properties.

Automated summary

The interactions between SbF6- and metal nanoclusters have been studied in this work, revealing the effects of SbF6- ions on the reconstruction and rearrangement of nanoclusters. The optical properties of these nanoclusters have also been explored, with Pt1Ag30-SbF6 displaying high performance in phosphorescence quantum yield and ECL efficiency compared to Pt1Ag28-SbF6.