Roles of Water Molecules in the Structures and Magnetic Properties of Coordination Polymers with a Dicarboxylate Ligand

Three new coordination polymers, {[M(nbpdc)(DMF)(H₂O)₂]·H₂O}_∞ (M = Co and Ni) and [Zn(nbpdc)(DMF)(H₂O)]_∞, were synthesized from 2-nitrobiphenyl-4,4′-dicarboxylate (nbpdc²⁻). The isomorphous Co(II) and Ni(II) compounds exhibited a two-dimensional coordination network in which the chains with single-water bridges and the chains with single-nbpdc²⁻ bridges intersected each other by sharing the metal ions. The coordination networks were connected with uncoordinated water molecules through hydrogen bonds. The rarely identified single-water-bridged coordination chain was reinforced by water-based intrachain hydrogen bonds. The single-water bridges mediated modest antiferromagnetic superexchange in both Co(II) and Ni(II) compounds and afforded a spin-canting structure for the Co(II) compound at low temperatures. Water molecules played a distinct structural role in the Zn(II) compound, which was a one-dimensional coordination polymer with single-nbpdc²⁻ bridges. Instead of bridging metal ions, each water molecule was coordinated to one metal ion and hydrogen-bonded to the coordination spheres of other two metal ions, resulting to an infinite ladderlike hydrogen-bonding motif. The ladders interlinked the nbpdc-bridged chains into a three-dimensional supramolecular architecture featuring the 5-conneted {4⁴.6⁴} net.