Martí-Rujas Javier
Dipartimento di Chimica Materiali e Ingegneria Chimica. "Giulio Natta", Politecnico di Milano, Via L. Mancinelli 7, 20131, Milan, Italy.
Commun Chem. 2025 Mar 27;8(1):92. doi: 10.1038/s42004-025-01493-3.
[2]-Catenanes formed from three-dimensional (3D) metal organic cages (MOCs) self-assembled from transition metals and organic ligands, hereafter called interlocked MOCs, constitute a relatively new class of mechanically interlocked materials (MIMs) that is receiving considerable research attention. This interest is mainly due to their esthetic synthetic aspects and mechanical properties, but also due to their potential applications in nanotechnological areas, including magnetic materials, guest selectivity, allosteric binding, or thermoresponsive behavior in elastomeric materials. In this article, a perspective on the research on interlocked MOCs (i.e., [2]-catenanes), covering from the first examples of interlocked MOCs to the latest research in this area is presented. The emphasis is in the synthetic methods used for their preparation and the structure‒function correlation aspects. The combination of experimental techniques in the solution state (i.e., NMR, ESI-MAS, etc.) and solid-state X-ray structural data, in combination with theoretical calculations have been very important to getting a rationalization of the experimental results. The described [2]-catenanes are formed from mechanically bonded hollow cages, therefore they can be exploited in host-guest chemistry applications typical from MOCs, with enhanced physical properties ranging from the mechanical bonds like enhanced cage's strength and dynamic behavior, which are needed for developing new smart functional materials.
由过渡金属和有机配体自组装而成的三维（3D）金属有机笼（MOCs）形成的[2]连环烷，以下称为互锁金属有机笼，构成了一类相对较新的机械互锁材料（MIMs），正受到广泛的研究关注。这种关注主要源于其美观的合成方面和机械性能，也源于它们在纳米技术领域的潜在应用，包括磁性材料、客体选择性、变构结合或弹性体材料中的热响应行为。在本文中，我们对互锁金属有机笼（即[2]连环烷）的研究进行了展望，涵盖了从互锁金属有机笼的首个实例到该领域的最新研究。重点在于用于其制备的合成方法以及结构 - 功能相关性方面。溶液状态下的实验技术（即核磁共振、电喷雾电离 - 质谱等）与固态X射线结构数据相结合，再加上理论计算，对于合理解释实验结果非常重要。所描述的[2]连环烷由机械键合的中空笼构成，因此它们可用于金属有机笼典型的主客体化学应用中，并具有增强的物理性质，范围从机械键如增强的笼强度和动态行为，这对于开发新型智能功能材料是必要的。
