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An investigation of the self-assembly of neutral, interlaced, triple-stranded molecular braids
Authors:Luan Xin-Jun  Cai Xue-Hua  Wang Yao-Yu  Li Dong-Sheng  Wang Cui-Juan  Liu Ping  Hu Huai-Ming  Shi Qi-Zhen  Peng Shie-Ming
Institution:Department of Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest University, Xi'an, Shaanxi, 710069, P.R. China.
Abstract:The synthesis and structures of six compounds prepared in two different systems have been explored with the purpose of isolating coordination polymers with interlaced triple-stranded molecular braid architectures. The dinuclear paddle-wheel units of Cu(2)(maa)(4)2 H(2)O] can be rationally tuned to form three classes of isomorphous compounds, namely Cu(2)(maa)(4)(bpp)] (1) (bpp=1,3-bis(4-pyridyl)propane, Hmaa=2-methylacrylic acid), Cu(3)(maa)(6)(bpp)(2)] (2), andCu(4)(maa)(8)(bpp)(4)(H(2)O)(2)]2 H(2)O (3), with a bridging bpp ligand, at controlled ligand-to-metal molar ratios, and lead to three coordination polymers having similar one-dimensional characteristics but different mono- and dinuclear nodes. Compound 1, with a bpp:Cu(2)(maa)(4)2 H(2)O] stoichiometry of 1:1, contains a zigzag chain containing dinuclear nodes, whereas polymer 2, with a bpp:Cu(2)(maa)(4)2 H(2)O] stoichiometry of 1.5:1, also adopts the topology of a zigzag chain but with both mono- and dinuclear nodes. Compound 3, with a bpp:Cu(2)(maa)(4)2 H(2)O] stoichiometry of 2:1, contains a neutral, interlaced, triple-stranded molecular braid, which is interwoven by three single-stranded meso-helical chains that contain only a mononuclear node. With the three aromatic chelating terminal ligands 2,2':6',2'-terpyridine (tpy), 1,10-phenanthroline (phen), and di(2-pyridyl)amine (dpa) we have also prepared three neutral complexes containing the linear, rigid bridging ligand biphenyl-4,4'-dicarboxylate (bpdc), namely Cd(bpdc)(tpy)]H(2)O (4), Cu(bpdc)(phen)(2)]4.25 H(2)O (5), and Cu(bpdc)(dpa)] (6). An infinite meso-helix is formed initially in 4, and then three of these chains assemble into a triple-stranded braid similar to that of 3. Complexes 5 and 6 have a mononuclear and a looped dinuclear structure, respectively. Compounds 3 and 4 are unusual examples of triple-stranded molecular braid coordination frameworks based on different types of co-ligands.
Keywords:cobalt  copper  crystal engineering  organic–inorganic hybrid composites  self‐assembly
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