Aliphatic and aromatic carboxylate divalent metal coordination polymers incorporating the kinked and hydrogen-bonding capable tethering ligand 4,4′-dipyridylamine

Numerous functional coordination polymer solids with diverse topologies have been constructed using the rigid rod tethering ligand 4,4′-bipyridine (4,4′-bpy). In contrast, the underlying structural topologies of coordination polymers based on the related diimine 4,4′-dipyridylamine (dpa) are often significantly different, due to its kinked donor disposition and hydrogen-bonding capability. In this review we discuss many of the divalent metal carboxylate/dpa dual-ligand coordination polymer phases recently prepared in our laboratory. One-, two- and three-dimensional structures with varying degrees of interpenetration have been observed; several unprecedented self-penetrated network topologies were generated. Synergistic interactions between metal coordination geometry, carboxylate donor disposition and binding mode and hydrogen bonding patterns mediated by the central amine of the dpa ligands play an important role in structure direction in this coordination polymer system.