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

Substitution of apical halide ligands in [{Re₆Seⁱ₈}X^a₆]^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.