This Account describes our efforts over the last decade to synthesize self-assembled metal–ligand cage complexes that display reactive functional groups on their interiors. This journey has taken us down a variety of research avenues, including studying the mechanism of reversible self-assembly, analyzing ligand self-sorting properties, post-assembly reactivity, molecular recognition, and binding studies, and finally reactivity and catalysis. Each of these individual topics are discussed here, as are the lessons learned along the way and the future research outlook. These self-assembled hosts are the closest mimics of enzymes to date, as they are capable of size- and shape-selective molecular recognition, substrate activation and turnover, as well as showing less common ‘biomimetic’ properties such as the ability to employ cofactors in reactivity, and alter the prevailing mechanism of the catalyzed reactions. 1 Introduction 2 Paddlewheels and Self-Sorting Behavior 3 First-Row Transition-Metal-Mediated Assembly: Sorting and Stereochemical Control 4 Post-Assembly Reactivity 5 Molecular Recognition and Catalysis 6 Conclusions and Outlook

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不，不是那样，另一种方式：在自组装宿主分子中创建活性位点

该帐户描述了我们在过去十年中为合成在其内部显示反应性官能团的自组装金属-配体笼络合物所做的努力。这一旅程使我们走上了各种研究途径，包括研究可逆自组装的机制、分析配体自分类特性、组装后反应性、分子识别和结合研究，最后是反应性和催化作用。这里讨论了这些单独的主题中的每一个，以及沿途学到的经验教训和未来的研究展望。这些自组装宿主是迄今为止最接近酶的模拟物，因为它们能够进行大小和形状选择性的分子识别、底物激活和转换，并显示出不太常见的“仿生”特性，例如使用辅助因子的能力在反应性，并改变催化反应的主要机制。1 介绍 2 桨轮和自分类行为 3 第一排过渡金属介导的组装：分类和立体化学控制 4 组装后反应 5 分子识别和催化 6 结论和展望