Nanocluster Transformation Induced by SbF6– Anions toward Boosting Photochemical Activities

The interactions between SbF 6 – 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 SbF 6 – anions, the step-by-step nanocluster evolutions from [Pt 1 Ag 28 (S-Adm) 18 (PPh 3 ) 4 ]Cl 2 (Pt 1 Ag 28 –Cl) to [Pt 1 Ag 28 (S-Adm) 18 (PPh 3 ) 4 ](SbF 6 ) 2 (Pt 1 Ag 28 –SbF 6 ) and then to [Pt 1 Ag 30 Cl 1 (S-Adm) 18 (PPh 3 ) 3 ](SbF 6 ) 3 (Pt 1 Ag 30 –SbF 6 ) have been mapped out with X-ray crystallography, with which atomic-level SbF 6 – 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 Pt 1 Ag 30 –SbF 6 nanocluster was ultrabright with a high phosphorescence quantum yield of 85% in N 2 -purged solutions, while Pt 1 Ag 28 nanoclusters were fluorescent with weaker emission intensities. Furthermore, Pt 1 Ag 30 –SbF 6 displayed superior ECL efficiency over Pt 1 Ag 28 –SbF 6, which was rationalized by its increased effectively exposed reactive facets. Both Pt 1 Ag 30 –SbF 6 and Pt 1 Ag 28 –SbF 6 demonstrated unprecedented high absolute ECL quantum efficiencies at sub-micromolar concentrations. This work is of great significance for revealing the SbF 6 – counterion effects on the control of both structures and luminescent properties.