Solvent-Induced Isomeric Cu13 Nanoclusters: Chlorine to Copper Charge Transfer Boosting Molecular Oxygen Activation in Sulfide Selective Oxidation

Isomers with minimal structural dissimilarities are promising research objects to obtain a comprehensive understanding of structure-property relationships; however, comparability of isomeric structures is a prerequisite. Herein, two quasi-structurally isomeric 13-nuclei copper nanoclusters (Cu NCs) (Cu13a and Cu13b) containing highly similar Cu₁₃ kernels and different arrangements of peripheral ligands were obtained using a solvent-induced strategy. The exotic chloride ion is shown to play a prominent role in inducing the selective formation of two quasi-isomers, where the comparative study to establish a structure-property relationship was realized. Due to the charge transition from chlorine to the copper core (X_(Cl)M_(Cu)CT), the molecular oxygen activation of Cu13a showed higher singlet oxygen (¹O₂) and lower superoxide radical (O₂^•-) yields compared to those of Cu13b, which gives it better catalytic selectivity for the ¹O₂ involved selective oxidation of sulfides. The present work not only offers a controllable strategy for the rational design and synthesis of quasi-structurally isomeric Cu NCs but also provides a pathway to boost catalytic selectivity by a halogen to metal core charge transition.