Synthesis, Structural Characterization, and Guest Exchange Properties of Hydrogen-Bonded Organic Frameworks Based on Bis(benzimidazole)ZnCl2 Complexes.

Hydrogen-bonded organic frameworks (HOFs) based on coordination compounds constitute a developing class of interesting porous materials. Herein, we report on the synthesis, crystal structures, and guest exchange properties of four HOFs based on zinc dichlorido complexes that bear a bis(benzimidazolyl)methane ligand (bis(benzimidazole)ZnCl2). The porous structures of these bis(benzimidazole)ZnCl2-based HOFs are characterized predominantly by intermolecular N-H···Cl hydrogen bonds in conjunction with π-π interactions. One of these HOFs was found to exchange guest molecules via single-crystal-to-single-crystal transformations with or without structural change. A single-crystal X-ray diffraction study revealed that the guest exchange accompanied by a structural change is induced by the cleavage of the N-H···Cl hydrogen bonds between the bis(benzimidazole)ZnCl2 complexes, followed by the formation of alternate hydrogen bonds with guest molecules. This result suggests that the use of weaker N-H···Cl hydrogen bonds than those typically used for the construction of HOFs (e.g., carboxylic acid dimers, N-heterocycles, and charge-assisted moieties) may represent a convenient strategy to synthesize flexible HOFs.