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  • Copper(I) coordination poly...
    Ni, Jia; Wei, Kai-Ju; Min, Yuanzeng; Chen, Yaowen; Zhan, Shunze; Li, Dan; Liu, Yangzhong

    Dalton transactions : an international journal of inorganic chemistry, 05/2012, Letnik: 41, Številka: 17
    Journal Article

    Reactions of CuX (X = Br(-), I(-) or CN(-)) with various types of 2,2'-dipyridylamine (dpa) derivatives have been performed via a hydrothermal-solvothermal method and the products have been structurally characterized by X-ray crystallography. Four ligands with different coordination motifs were employed in the reactions, including angular N,N,N',N'-tetra(2-pyridyl)-2,6-pyridinediamine (tppda); linear N,N,N',N'-tetra(2-pyridyl)-1,4-phenylenediamine (tppa) and N,N,N',N'-tetra(2-pyridyl)biphenyl-4,4'-diamine (tpbpa); and star-shaped tris-4-(2,2'-dipyridylamino)-phenylamine (tdpa), which yielded eight copper(I) complexes exhibiting different stoichiometries of Cu-dpa and variable coordination modes of dpa. The compound Cu(2)(tppda)(μ-I)(2)(n) (1) forms a one dimensional (1D) coordination polymer exclusively through double μ(2)-I bridges, which arranges to two dimensional (2D) metal-organic frameworks (MOFs) via the face-to-face π···π stacking interactions from pyridyl rings. The compound Cu(6)(tppa)(μ(3)-Br)(6)(n) (2) forms a 2D network linked through multiple μ(3)-Br bridges. The compound Cu(2)(tppa)(μ-CN)(2)(n) (3) is also a 2D MOF containing 1D (CuCN)(n) chains. The compounds Cu(tpbpa)Br(n) (4) and Cu(4)(tpbpa)(2)(μ-I)(4)(n) (5) display two different 1D assemblies: a zig-zag chain for 4 and a linear structure for 5. The compound Cu(4)(tpbpa)(μ-CN)(4)(n) (6) shows a pseudo-4,8(2) topological net, while the compound Cu(8)(tpbpa)(μ-CN)(8)(n)·2nH(2)O (7) exhibits a three-dimensional (3D) framework containing a ···PM··· double helical structure, although both of them contain (CuCN)(n) chains. The compound Cu(2)(tdpa)(μ-I)(2)(n) (8) is a zig-zag chain based on the star-shaped molecule tpda, in which one of three dpa-arms is free of coordination to metal ions. All complexes exhibit luminescence in the solid state.