Zr-carboxylate metal-organic frameworks (MOFs) are structurally robust materials, in part due to their strong coordination bonds. The regioselective Zr–O bond cleavage and formation between 3D architectures are thus challenging and are heretofore unexplored. In this work, by introducing highly flexible 18-crown-6-ether functionalities into a homochiral Zr-MOF, we report an unprecedented topology transition in which a 4,10-connected framework undergoes a rapid solid-state transition into a thermodynamically more stable 4,8-connected analog by a regioselective-linker-elimination under ambient conditions. The transition process was unambiguously unraveled by single-crystal and powder X-ray diffraction studies, and we proposed a possible transition mechanism based on various control experiments and theoretical calculations. The excellent chemical stability and substantially expanded porosity and pore apertures endowed the transformed chiral MOF with an exceptional capacity for the enantioadsorptive and solid-phase extractive separation of the racemic drug molecule of lansoprazole with 98% ee and 93% ee, respectively.

Zr-羧酸盐金属有机骨架（MOF）是结构坚固的材料，部分原因是它们具有很强的配位键。因此，在3D结构之间区域选择性Zr–O键的断裂和形成是具有挑战性的，迄今为止尚未得到探索。在这项工作中，通过向同手性Zr-MOF中引入高度灵活的18-冠-6-醚功能，我们报告了前所未有的拓扑转变，其中4,10连接的框架经历了快速固态转变成热力学上更稳定的转变在环境条件下通过区域选择性接头消除4,8连接的模拟物。单晶和粉末X射线衍射研究清楚地阐明了转变过程，我们基于各种控制实验和理论计算提出了可能的转变机理。