| Abstrakt: |
Six new coordination polymers (CPs), namely, [Mn2(OH)(TZI)(DMA)] (1), [Cu2(OH)(TZI)(DMA)]·3.5H2O (2), [Co2(OH)(TZI)(H2O)2] (3), [Zn2(OH)(TZI)(2,2′-bpy)]·H2O (4), [Zn2(OH)(TZI)(phen)]·2H2O (5) and [Zn2(OH)(TZI)(4,4′-bpy)0.5] (6), (H3TZI = 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 M4(μ3-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 corner-sharing Co3(μ3-OH) triangle Δ-chains in which Co(ii) ions are bridged by mixed (μ4-tetrazolate)(μ3-OH)(μ2-COO) bridges. CPs 4–6 were synthesized by the reactions of the H3TZI ligands, Zn(NO3)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 (μ2-tetrazolate)(μ2-OH) bridges are connected by the TZI spacers to produce a 2D framework. Differently, in 5, the dinuclear motifs with mixed double (μ2-COO)(μ2-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 (44·62)(412·58·616·76·83) 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. [ABSTRACT FROM AUTHOR] |
