Three New MOFs Induced by Organic Linker Coordination Modes: Gas Sorption, Luminescence, and Magnetic Properties

Abstract By using a new 4,6‐bis(imidazol‐1‐yl) isophthalic acid ligand (H 2 bimip) with imidazolyl and carboxyl bifunctional groups, three new MOFs, [Co(bimip)(H 2 O) 0.5 ] ⋅ 0.5 H 2 O ( 1 ), [Zn(bimip)] ( 2 ), and [Mn(bimip)(H 2 O) 2 ] ⋅ H 2 O ( 3 ), have been solvothermally synthesized in different solvent systems. H 2 bimip displays three different coordinated modes through the imidazolyl and carboxyl groups, and different cis – cis and trans – cis configurations, which result in distinct 3D topological frameworks: a (4,8)‐connected scu net for 1 ; a twofold interpenetrated (4,4)‐connected pts net for 2 ; and a four‐connected sra net for 3 . Compounds 1 and 3 show antiferromagnetic properties, and 2 emits strong solid‐state blue luminescence. Compound 1 shows good chemical stability in acidic and basic environments and in boiling water. Additionally, the polar channels in 1 , which are decorated by uncoordinated carboxylate O atoms and imidazolyl fragments, allow it to adsorb CO 2 molecules selectively over CH 4 , and the CO 2 binding sites in the framework were distinguished by molecular simulations.