Divalent Metal Aliphatic Tricarboxylate Dipyridylamine Coordination Polymers with New or Rare Binodal Topologies

Hydrothermal synthesis has afforded four divalent metal coordination polymers containing the aliphatic tricarboxylates tricarballylate (tca) or trans-aconitate (acon) and the kinked tethering co-ligand 4,4′-dipyridylamine (dpa). Diverse structural topologies are evident across this series, with coordination geometry and carboxylate binding mode serving important structure-directing roles. {[Cd2(tca)2(Hdpa)2]·7H2O}n (1) possesses one-dimensional (1-D) ribbon motifs with pendant Hdpa+ ligands and a new 4-connected supramolecular topology, along with co-crystallized water molecule tapes. {[Cd3(acon)2(dpa)2(H2O)2]·4H2O}n (2) has a 4,4-connected binodal lattice with frl (4264)4(6482) topology, while the structurally related phase {[Zn3(tca)2(dpa)2]·2H2O}n (3) has a 4,4-connected binodal lattice with a novel (426282)4(6284) topology. [Cu(Htca)(dpa)]n (4) manifests a 3,5-connected binodal net with rare (4.62)(4.6683) topology. Thermal stability of these materials is discussed. Complexes 1–3 undergo blue-violet light emission on excitation with ultraviolet light.