Syntheses, Structures, and Characteristics of Six Coordination Polymers Based on 1,4‐Bis(imidazol‐1‐yl)benzene and Isophthalates Containing Coordination‐Inert Substituents

Hydrothermal reactions of 1,4‐bis(imidazol‐1‐yl)benzene (bimb) and either 5‐hydroxyisophthalic acid (HO‐H 2 ip) or 5‐methoxyisophthalic acid (MeO‐H 2 ip), as well as transition metal salts, gave rise to six new coordination polymers: [Zn 2 (bimb)(H 2 O)(HO‐ip) 2 ] n ( 1 ), [Zn(bimb)(MeO‐ip)] n · (H 2 O) n ( 2 ), [Mn 2 (bimb) 2 (HO‐ip) 2 ] n ( 3 ), [Mn 2 (bimb) 2 (H 2 O) 2 (MeO‐ip) 2 ] n ( 4 ), [Cu 2 (bimb) 2 (MeO‐ip) 2 ] n · (H 2 O) 3 n ( 5 ), and [Co(bimb)(H 2 O)(MeO‐ip)] n · (DMF) 0.5 n · (H 2 O) n ( 6 ). Their structures have been defined by single‐crystal X‐ray diffraction analyses, IR spectra, elemental analyses and thermogravimetric analyses. Complex 1 is a 2D coordination network consisting of μ‐oxygen‐bridged dinuclear Zn II units, whereas 2 is an interdigitating 2D layer. Zn II ions in 1 and 2 have a distorted tetrahedral geometry, and two independent HO‐ip and two bimb moieties in the dinuclear unit of 1 form π ··· π stacking interactions. Complexes 3 and 4 are 2D layers consisting of dinuclear Mn II carboxylate units; bimb in an anti conformation serves as an exo ‐bidentate ligand in 3 , whereas in 4 it acts as a terminal ligand, filling void space. Bis‐monodentate MeO‐ip in 5 connects Cu II ions into a 3D coordination network, whereas MeO‐ip in 6 bridges between two Co II ions to form a 2D layer, with the strong hydrogen bonds between water molecules of the adjacent 2D layers generating a 2D supramolecular bilayer. The dinuclear Mn II units in 3 and 4 are well separated by organic ligands, and make up the basic magnetic units. Temperature‐dependent magnetic susceptibility analyses show the existence of antiferromagnetic interaction in 3 and 4 .