Structurally diverse divalent metal pyromellitate coordination polymers with very long spanning dipyridylamide ligands

Abstract Hydrothermal reaction of divalent metal nitrates, pyromellitic acid (pymH 4 ), and either 1,6-hexanediaminebis(nicotinamide) (hbn) or 1,6-hexanediaminebis(isonicotinamide) (hbin) afforded crystalline coordination polymers whose dimensionality depends synergistically on the dipyridylamide nitrogen donor disposition and metal coordination environment. These new phases were structurally characterized via single-crystal X-ray diffraction. [Cd(pymH 2 )(hbn)(H 2 O) 2 ] n ( 1 ) and [Co(pymH 2 )(hbn)(H 2 O) 2 ] n ( 2 ) display isostructural (4,4) grid topologies with [M(pymH 2 )(H 2 O) 2 ] n chains pillared by hbn ligands. {[Cu 2 (pym)(hbn)(H 2 O) 2 ]·2H 2 O} n ( 3 ) manifests a 3D 3,4-connected network with a rare (8 3 ) 2 (8 6 ) topology built from the hbn pillaring of [Cu 2 (pym)(H 2 O)] n layer motifs. {[Zn 2 (pym)(hbin) 2 (H 2 O)]·H 2 O} n ( 4 ) shows a 1D ribbon motif based on [Zn 2 (OCCCCO) 2 ] 14-membered circuits. {[Ni 2 (pym)(hbin)(H 2 O) 4 ]·3H 2 O} n ( 5 ) exhibits 3,4-connected layer motifs with rare {4.6 2 } 2 {4 2 6 2 8 2 } topology. Luminescent behavior in 1 and 4 is ascribed to intra-ligand molecular orbital transitions. These phases were also surveyed for the ability to detect nitrobenzene in ethanol suspension. Thermal decomposition behavior of 1 – 5 is also discussed herein.