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.