Copper(i) coordination polymers of 2,2-dipyridylamine derivatives: syntheses, structures, and luminescenceCCDC 279821, 773756773762. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c2dt12032a

• Main Authors: Ni, Jia, Wei, Kai-Ju, Min, Yuanzeng, Chen, Yaowen, Zhan, Shunze, Li, Dan, Liu, Yangzhong
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c2dt12032a

Reactions of CuX (X = Br , I or CN ) with various types of 2,2-dipyridylamine (dpa) derivatives have been performed via a hydrothermalsolvothermal 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)-phenyl]amine ( tdpa ), which yielded eight copper( i ) complexes exhibiting different stoichiometries of Cudpa and variable coordination modes of dpa. The compound [Cu 2 ( tppda )(-I) 2 ] n ( 1 ) forms a one dimensional (1D) coordination polymer exclusively through double 2 -I bridges, which arranges to two dimensional (2D) metalorganic frameworks (MOFs) via the face-to-face stacking interactions from pyridyl rings. The compound [Cu 6 ( tppa )( 3 -Br) 6 ] n ( 2 ) forms a 2D network linked through multiple 3 -Br bridges. The compound [Cu 2 ( tppa )(-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 (-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 )(-CN) 4 ] n ( 6 ) shows a pseudo-4,8 2 topological net, while the compound [Cu 8 ( tpbpa )(-CN) 8 ] n 2 n H 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 )(-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. The reaction of CuX (X = Br , I or CN ) with various types of 2,2-dipyridylamine (dpa) derivatives has been performed by using a hydrothermalsolvothermal method. They exhibit different stoichiometries of Cudpa and variable coordination modes of dpa by controlling the reaction conditions.