Framework-Isomeric Metal–Organic Frameworks Built from Supermolecular Building Blocks for High Iodine Capture

The supermolecular building block approach is powerful in constructing hierarchically porous metal–organic frameworks (MOFs). However, the structural diversity of these extended frameworks built from the same building blocks has never been explored. Herein, we propose a strategy by synergistically tuning the extending direction of metal–organic polyhedra (MOPs) and the linker conformation to achieve MOFs with framework isomerism. Six novel MOFs (CCNUF-1–6) based on an octahedral MOP and different tritopic pyridine-based linkers were successfully synthesized, among which the structural diversity increased with increasing linker flexibility. The topologies (sql, kgd, and rtl) of these materials are unprecedented in MOP-based MOFs. Moreover, highly porous CCNUF-2–6 showed remarkable iodine uptake capacities in the range of 2.51 to 3.11 g g–1. This study emphasizes the potential of MOPs containing open metal sites as versatile platforms for the development of diversified hierarchically porous MOFs with enhanced functional properties.