Solvent-Induced Isomeric Cu<sub>13</sub> Nanoclusters: Chlorine to Copper Charge Transfer Boosting Molecular Oxygen Activation in Sulfide Selective Oxidation.
basic_science · Level V
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- Record sourced from PubMed, PMID 35700320.
- Also identified by DOI 10.1021/acsnano.2c02885.
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Abstract
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) (<b>Cu13a</b> and <b>Cu13b</b>) containing highly similar Cu<sub>13</sub> 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<sub>(Cl)</sub>M<sub>(Cu)</sub>CT), the molecular oxygen activation of <b>Cu13a</b> showed higher singlet oxygen (<sup>1</sup>O<sub>2</sub>) and lower superoxide radical (O<sub>2</sub><sup>•-</sup>) yields compared to those of <b>Cu13b</b>, which gives it better catalytic selectivity for the <sup>1</sup>O<sub>2</sub> 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.