Self-Assembled Microporous M-HOFs Based on an Octahedral Rhenium Cluster with Benzimidazole

Substitution of apical halide ligands in [{Re6Sei8}Xa6]3– (X = Cl, Br) by benzimidazole (bimzH) accompanied by a self-assembly process leads to the formation of microporous Re6-based hydrogen-bonded organic frameworks (Re6-HOFs) constructed on N–H···X hydrogen bonds and π–π-stacking interactions between bimzH ligands. Re6-HOFs demonstrate sorption properties with a Brunauer–Emmett–Teller surface area of up to 443 m2 g–1 and luminescence with a quantum yield and an emission lifetime of up to 0.16 and 16 μs, respectively. The compounds obtained complement small groups of transition-metal cluster-based HOFs, which are a perspective for the development of multifunctional frameworks.