Abstract
Despite their scarcity due to synthetic challenges, supertetrahedron-based metal-organic frameworks (MOFs) possess intriguing architectures, diverse functionalities, and superb properties that make them in-demand materials. Employing a new window-space-directed assembly strategy, a family of mesoporous zeolitic MOFs have been constructed herein from corner-shared supertetrahedra based on homometallic or heterometallic trimers [M-3(OH/O)(COO)(6)] (M-3 = Co-3, Ni-3 or Co2Ti). These MOFs consisted of close-packed truncated octahedral cages possessing a sodalite topology and large beta-cavity mesoporous cages (similar to 22 angstrom diameter) connected by ultramicroporous apertures (similar to 5.6 angstrom diameter). Notably, the supertetrahedron-based sodalite topology MOF combined with the Co2Ti trimer exhibited high thermal and chemical stability as well as the ability to efficiently separate acetylene (C2H2) from carbon dioxide (CO2).