Structural Fluxionality of Surface Motifs in Positional Isomeric Au₁₄Cd₂ Clusters Enables Switchable O–O Bond Activation Pathways

However, up to now, the packing model of the core and motif has typically been one-to-one. Herein, we present positional isomeric nanoclusters, Au₁₄Cd₂-1 and Au₁₄Cd₂-2, which feature an identical Au₁₃ icosahedral kernel but differ exclusively in their surface motif arrangements, leading to distinct electronic distributions.

This inherent structural fluxionality enables their reversible interconversion mediated by boranes. Capitalizing on distinct metal charge distributions of the isomers, we employed styrene oxidation (highly sensitive to metal valence states) as a mode to probe their catalytic performance. The results show that the electron-deficient Au₁₄Cd₂-1 achieves high conversion (93.1%) with epoxide selectivity (77.3%), whereas the electron-rich Au₁₄Cd₂-2 gives lower conversion (36.8%) but high benzaldehyde selectivity (88.9%).