Effect of Polycarboxylate Coligands from Linear to V-shaped Cu^IICoordination Polymers Based on a Rigid Tripodal Ligand

Abstract The layered Cu II coordination polymer {[Cu(tib) 2 (H 2 O) 2 ](NO 3 ) 2 } ( 1 ) based on the rigid tripodal 1,3,5‐tris(1‐imidazolyl)benzene (tib) ligand was synthesized by hydrothermal methods. By introducing different polycarboxylate coligands from linear 4,4′‐biphthalic acid (H 4 L 1 ) to V‐shaped thiophene‐2,5‐dicarboxylic acid (H 2 L 2 ), two new copper(II) compounds were obtained, namely, {Cu(tib)(H 2 L 1 )(H 2 O) · 3H 2 O} ( 2 ) and {Cu(tib)(L 2 ) · 3H 2 O} ( 3 ). X‐ray diffraction analyses reveal that compound 2 displays a hydrogen‐bonded three‐dimensional (3D) supramolecular structure, in which protonated {H 2 L 1 } 2– ligands occupy some coordination sites around the metal atoms to form one‐dimensional (1D) chain by blocking the formation of two‐dimensional (2D) Cu‐tib layer as in compound 1 . Interestingly, compound 3 features a rare twofold interpenetrating binodal seh ‐3,5‐ P 4 3 2 1 2 topological network by synergistic effect of V‐shaped carboxylate group and functionally complementary N‐donor ligand. These compounds were characterized by elemental analyses, thermogravinetric analyses, and photoluminescent spectroscopy.