The rational synthesis of advanced porous materials with performances mimicking those of biological proteins remains challenging. Evidently, metal-organic frameworks with dense, rigid aromatic motifs hinder the creation of adaptable cavities with superior guest-to-framework interactions. Herein, a zirconium macrocyclic framework, named metal-macrocyclic framework (MMCF)-6, featuring an adaptive cavity, was constructed using a cyclam-based linker. The vacant yet adaptable cyclam cavity in MMCF-6 renders it capable of precisely recognizing Pd²⁺ in aqueous solution with a high uptake capacity of 326 mg g^-1 and extraordinary recovery efficiency of >99.99%. The characteristic proteomimetic behavior of MMCF-6, that is, guest-induced fit during the Pd²⁺ recovery, was unveiled by combined studies of X-ray crystallography, extended X-ray absorption fine structure, and density functional theory, which provided unambiguous confirmation of the cyclam macrocycle’s allosteric behavior accountable for the excellent Pd capture performance. Our work herein opens a new avenue by incorporating semi-rigid cavities into framework materials for efficient host-guest chemistry.

合理合成具有模仿生物蛋白质性能的先进多孔材料仍然具有挑战性。显然，具有致密、刚性芳香图案的金属有机框架阻碍了具有优异的客体与框架相互作用的适应性空腔的创建。在此，使用基于cyclam的连接体构建了一种锆大环骨架，称为金属大环骨架（MMCF）-6，具有自适应空腔。 MMCF-6中空的但适应性强的仙客来腔使其能够精确识别水溶液中的Pd ^{2+ ，具有高达326 mg g -1}的高吸收容量和> 99.99%的非凡回收率。通过 X 射线晶体学、扩展 X 射线吸收精细结构和密度泛函理论的综合研究，揭示了MMCF-6 的特征蛋白质模拟行为，即 Pd ²⁺恢复过程中的客体诱导拟合，这提供了明确的解释。确认了cyclam大环的变构行为导致了优异的Pd捕获性能。我们的工作通过将半刚性空腔合并到框架材料中以实现有效的主客体化学反应开辟了一条新途径。