Copper(i) coordination polymers of 2,2′-dipyridylamine derivatives: syntheses, structures, and luminescence

• DOI: 10.1039/c2dt12032a
• Publication Date: 2012-03-14T10:00:50Z
• Authors: Jia Ni; Kai-Ju Wei; Yuanzeng Min; Yaowen Chen; Shunze Zhan; Dan Li; Yangzhong Liu
• Keywords: Coordination polymer; Tetra; Stoichiometry

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