Zhang Chengkai, Wang Zhi, Si Wei-Dan, Wang Liuyi, Dou Jian-Min, Gao Zhi-Yong, Tung Chen-Ho, Sun Di
School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Ji'nan 250100, People's Republic of China.
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, and School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252000, People's Republic of China.
ACS Nano. 2022 Jun 28;16(6):9598-9607. doi: 10.1021/acsnano.2c02885. Epub 2022 Jun 14.
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) ( and ) containing highly similar Cu 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 (XMCT), the molecular oxygen activation of showed higher singlet oxygen (O) and lower superoxide radical (O) yields compared to those of , which gives it better catalytic selectivity for the O 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.
结构差异最小的异构体是全面理解结构-性质关系的有前景的研究对象；然而，异构体结构的可比性是一个先决条件。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）（ 和 ），它们含有高度相似的铜核以及不同排列的外围配体。结果表明，奇特的氯离子在诱导两种准异构体的选择性形成中起显著作用，在此实现了建立结构-性质关系的对比研究。由于氯到铜核的电荷转移（XMCT），与 相比， 的分子氧活化显示出更高的单线态氧（O）产率和更低的超氧自由基（O）产率，这使其对涉及硫化物选择性氧化的O具有更好的催化选择性。本工作不仅为合理设计和合成准结构异构的Cu NCs提供了一种可控策略，还提供了一条通过卤素到金属核电荷转移来提高催化选择性的途径。
