Six novel coordination polymers based on the 5-(1H-tetrazol-5-yl)isophthalic acid ligand: structures, luminescence, and magnetic properties

Six new coordination polymers (CPs), namely, [Mn-2(OH)(TZI)(DMA)] (1), (Cu-2(OH)(TZI)DMA)]center dot 3.5H(2)O (2), [Co-2(OH)(TZI)(H2O)(2)] (3), (Zn2(OFI)(TZI)(2,2'-bpy)]center dot H2O (4), (Zn-2(OH)(TZI)(phen)]center dot 2H(2)O (5) and [Zn-2(OH)(TZI)(4,4'-bpy)(0.)(5)] (6), (H(3)TZI = 5-(4-(tetrazol-5-yl)phenyl)isophthalic acid, 2,2'-bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline, 4,4'-bpy = 4,4'-bipyridine, and DMA = N,N-dimethylacetamide), have been synthesized under solvo-/hydrothermal conditions. Both 1 and 2 exhibit 3D structures containing butterfly-shaped tetranuclear M-4(mu(3)-OH)(2) clusters as secondary building units (SBUs). In 1, the SBUs are connected into 1D chains by the tetrazolate groups of the TZI ligands and the chains are further interlinked into a (4,8)-connected 3D net by the TZI spacers. In 2, the SBUs are directly connected by TZI to give a (3,6)-connected 3D framework. CP 3 features a double-layered structure based on cornersharing Co-3(mu(3)-OH) triangle Delta-chains in which Co(II) ions are bridged by mixed (mu(4)-tetrazolate)(mu(3)-OH)(mu(2)-COO) bridges. CPs 4 6 were synthesized by the reactions of the H(3)TZI ligands, Zn(NO 3 ) 2 and three different N-donor auxiliary ligands. The auxiliary ligands change from chelating ligands (2,2'-bpy, phen) to 4,4'bpy, which leads to remarkable structural changes from 2D to 3D. CPs 4 and 5 display 2D structures with dinuclear motifs as SBUs. In 4, the dinuclear motifs with mixed double (mu(2)-tetrazolate)(mu(2)-OH) bridges are connected by the TZI spacers to produce a 2D framework. Differently, in 5, the dinuclear motifs with mixed double (mu(2)-COO)(mu(2)-OH) bridges are interlinked into a 2D framework with a (4,4)-connected net topology. In 6, the square Zn4O4 clusters are interlinked by the organic ligands into a 3D framework with a (4,10)-connected (4(4).6(2))(4(12). 5(8).6(16).7(6).8(3)) topology. Magnetic studies indicate that CPs 1-3 exhibit antiferromagnetic coupling. Further magnetic measurement demonstrates that CPs 1 and 3 show no magnetic ordering above 2 K. CPs 4-6 exhibit strong luminescence with different energies in the solid state at room temperature.