Effect of pendant arm position and length on the structure and properties of nickel aromatic dicarboxylate coordination polymers incorporating a kinked organodiimine

Abstract Hydrothermal synthesis has afforded three nickel coordination polymers incorporating both aromatic dicarboxylates and the kinked and hydrogen bonding capable organodiimine 4,4′-dipyridylamine (dpa). These were characterized by single-crystal X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. [Ni(1,2-phda)(dpa)(H 2 O)] n (1,2-phda = 1,2-phenylenediacetate, 1 ) displays (4,4) rhomboid grid-like 2D layers that aggregate into 3D through O–H⋯O hydrogen bonding. Shortening one of the pendant arms of the dicarboxylate ligand resulted in a shift to (6,3) herringbone style 2D coordination layer motifs in {[Ni(hmph)(dpa)] · 1.33H 2 O} n (hmph = homophthalate, 2 ), which stack in an AA′B pattern. [Ni(1,3-phda)(dpa)(μ-H 2 O) 0.5 ] n (1,3-phda = 1,3-phenylenediacetate, 3 ) manifests a canted primitive cubic type coordination polymer lattice constructed from dinuclear {Ni 2 (μ-H 2 O)} kernels linked into 3D through tethering 1,3-phda and dpa ligands. Analysis of the variable temperature magnetic susceptibility of 3 indicated the presence of antiferromagnetic superexchange within its dinuclear units ( g  = 2.290(2), J  = −4.21(2) cm −1 ).