Direct Conversion of Benzothiadiazole to Benzimidazole: New Benzimidazole‐Derived Metal–Organic Frameworks with Adjustable Honeycomb‐Like Cavities

: Up to now, the direct conversion of the thiadiazole ring to other heterocyclic rings has been a very challenging task. Herein, a CdII -mediated alcohol-substitution strategy for direct conversion from benzothiadiazole to benzimidazole is reported. Experimental and molecular modeling studies on the role of the chelated metal ion in this in situ alcohol-substitution reaction revealed that it serves as an all-rounder that is involved in the insertion of alcohol, activation of the thiadiazole ring by coordinative interaction, and the sulfur-extrusion process. Interestingly, the insertion of alcohol occurs much earlier than the sulfur-extrusion process, supported by a water-mediated proton-transfer process. This strategy also is suitable for constructing new benzimidazole-derived MOFs [Cd2 (HMBIDC2- )2 ]⋅4 H2 O (Cd-BID-MOF-1, HMBIDC2- =2-methyl-1H-benzimidazole-4,7-dicarboxylate) and [Cd2 (HPBIDC2- )2 ]⋅1/3 H2 O (Cd-BID-MOF-2, HPBIDC2- =2-(3-hydroxypropyl)-2H-benzimidazole-4,7-dicarboxylate). Because the terminal hydroxyl group on the imidazole ring protrudes into the circular channel in rhombohedral Cd-BID-MOF-2, the cavity is closer to hydrophilic than the honeycomb-like cavity in Cd-BID-MOF-1 with similar 3D structure. This rare observation will provide a new strategy to develop in situ ligand-reaction synthesis of functional MOFs and useful chelation-assisted catalytic reactions in heteroaromatic chemistry.