Macrocyclic ligands have been extensively applied to recognize single metal ions with high selectivity and good affinity based on the size-match principle. The resulting metal–macrocycle complexes play a significant role in mimicking the function of natural metal ion carriers and understanding and reproducing the catalytic activity of metalloenzymes. Because of the known macrocyclic effect, those single metal–macrocycle adducts often show an enhanced kinetic and thermodynamic stability in comparison with their open-chain analogues. By virtue of such extraordinary coordination properties of macrocyclic ligands, it is expected that larger macrocycles with multiple coordination sites could properly act as an outer scaffold to direct the formation of multiatom species inside, such as polynuclear metal cluster aggregates, whose assembly may largely depend on the template positioning of coordinative atoms in the macrocyclic ring. Thus, the employment of polydentate macrocyclic ligands may provide a convenient tool to access polynuclear metal clusters in a controllable way.

中文翻译：

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大环环抱的多核金属簇：可控制的合成，反应性研究和应用

基于尺寸匹配原理，大环配体已被广泛应用于以高选择性和良好亲和力识别单一金属离子。由此产生的金属-大环络合物在模仿天然金属离子载体的功能以及理解和再现金属酶的催化活性方面起着重要作用。由于已知的大环效应，那些单金属-大环加合物与其开链类似物相比通常显示出增强的动力学和热力学稳定性。借助大环配体的非凡配位性能，可以预期具有多个配位点的较大大环可以适当地充当外部支架，以指导内部的多原子物种（例如多核金属簇聚集体）的形成，它的组装在很大程度上取决于大环上配位原子的模板位置。因此，采用多齿大环配体可以提供一种方便的工具，以可控制的方式进入多核金属簇。