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.

中文翻译：

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溶剂诱导的异构 Cu13 纳米团簇：氯到铜的电荷转移促进硫化物选择性氧化中的分子氧活化

具有最小结构差异的异构体是有前途的研究对象，可以全面了解结构-性质关系；然而，异构结构的可比性是先决条件。在此，使用溶剂诱导策略获得了两个准结构异构的 13 核铜纳米团簇 (Cu NCs)（Cu13a和Cu13b），它们含有高度相似的 Cu _{13核和不同排列的外围配体。}外来氯离子被证明在诱导两种准异构体的选择性形成中起着重要作用，实现了建立结构-性质关系的比较研究。由于从氯到铜芯的电荷转移 (X _(Cl) M_{(Cu) CT)，与}Cu13b相比， Cu13a的分子氧活化显示出更高的单线态氧 ( ¹ O ₂ ) 和更低的超氧自由基 (O ₂ ^•– ) 产率，这使其对所涉及的¹ O ₂具有更好的催化选择性硫化物的选择性氧化。目前的工作不仅为准结构异构 Cu NC 的合理设计和合成提供了可控策略，而且还提供了通过卤素到金属核电荷转变来提高催化选择性的途径。