Hierarchical assembly of a Ti24 metal-organic polyhedron via kinetic trapping of intermediates

The synthesis of high-nuclearity titanium metal-organic polyhedra (Ti-MOPs) has remained a formidable challenge due to the high oxophilicity and hydrolysis susceptibility of Ti4+ ions. Herein, we report a Ti24 MOP with a truncated octahedron (tro) topology, which represents the highest nuclearity Ti-MOP reported to date. Beyond structural characterization, we introduce a pathway intervention strategy using Ni2+ as a kinetic modulator to trap and structurally characterize two key intermediates—a Ti12 macrocycle and a Ti12 (6-4-6) module. These intermediates outline a hierarchical assembly pathway from simple precursors to Ti24 MOP. Furthermore, we demonstrate that this process is governed by a coordination lability gradient between Ti4+ and Ni2+, providing an effective strategy for directing supramolecular complexity. This Ti-MOP exhibits permanent microporosity, gas separation, and post-assembly modification capability. This work transforms a synthetic challenge into a strategic advantage, offering a blueprint for the rational assembly of complex metal-organic architectures. Here authors report the highest nuclearity Ti24 metal-organic polyhedral to date, with a truncated octahedron topology for potential gas separation.