Fang Jun-Jie, Liu Zheng, Shen Yang-Lin, Xie Yun-Peng, Lu Xing
State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology Wuhan 430074 China
Chem Sci. 2023 Oct 13;14(44):12637-12644. doi: 10.1039/d3sc04682f. eCollection 2023 Nov 15.
A comparative study of structure-property relationships in isomeric and isostructural atomically precise clusters is an ideal approach to unravel their fundamental properties. Herein, seven high-nuclearity copper(i) alkynyl clusters utilizing template-assisted strategies were synthesized. Spherical Cu and Cu clusters are formed with a [M@(V/PO)] (M: Cu, Na, K) skeleton motif, while peanut-shaped Cu clusters feature four separate PO templates. Experiments and theoretical calculations suggested that the photophysical properties of these clusters are dependent on both the inner templates and outer phosphonate ligands. Phenyl and 1-naphthyl phosphate-protected clusters exhibited enhanced emission features attributed to numerous well-arranged intermolecular C-H⋯π interactions between the ligands. Moreover, the electrocatalytic CO reduction properties suggested that internal PO templates and external naphthyl groups could promote an increase in C products (CH and CHOH). Our research provides new insight into the design and synthesis of multifunctional copper(i) clusters, and highlights the significance of atomic-level comparative studies of structure-property relationships.
对同分异构和同构的原子精确簇合物的结构-性质关系进行比较研究，是揭示其基本性质的理想方法。在此，利用模板辅助策略合成了七个高核铜（I）炔基簇合物。球形的铜和铜簇合物形成了[M@(V/PO)]（M：Cu、Na、K）骨架 motif，而花生形的铜簇合物具有四个独立的PO模板。实验和理论计算表明，这些簇合物的光物理性质既取决于内部模板，也取决于外部膦酸酯配体。苯基和1-萘基磷酸酯保护的簇合物表现出增强的发射特征，这归因于配体之间大量排列良好的分子间C-H⋯π相互作用。此外，电催化CO还原性质表明，内部PO模板和外部萘基可以促进C产物（CH和CHOH）的增加。我们的研究为多功能铜（I）簇合物的设计和合成提供了新的见解，并突出了结构-性质关系的原子水平比较研究的重要性。
