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. {[Cd 2 (tca) 2 (Hdpa) 2 ]·7H 2 O} 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. {[Cd 3 (acon) 2 (dpa) 2 (H 2 O) 2 ]·4H 2 O} n ( 2 ) has a 4,4-connected binodal lattice with frl (4 2 6 4 ) 4 (6 4 8 2 ) topology, while the structurally related phase {[Zn 3 (tca) 2 (dpa) 2 ]·2H 2 O} n ( 3 ) has a 4,4-connected binodal lattice with a novel (4 2 6 2 8 2 ) 4 (6 2 8 4 ) topology. [Cu(Htca)(dpa)] n ( 4 ) manifests a 3,5-connected binodal net with rare (4.6 2 )(4.6 6 8 3 ) topology. Thermal stability of these materials is discussed. Complexes 1 – 3 undergo blue-violet light emission on excitation with ultraviolet light.