| Coordination polymers as functional solid materials with specific network topologies are of great interest due to their fascinating molecular structures and potential applications to magnetism, nonlinear optical materials, electrical conductivity, ion exchange, separation, biology, and catalysis. Especially, the assembly of organic molecules and metal-ion building blocks can yield a new generation of multi-dimensional networks, which contain channels, or cavities of various sizes and shapes. At present, many chemical works have devoted most of their time to construct transition metal polymers with especial property and novel architecture and suptramolecular networks by hydrogen bond and π-π interaction. In order to satisfy the increasing demands of multifunctional materials, self-assembly in hydrothermal synthesis, as an effective synthetic strategy, is used comprehensively to synthesize stable coordination polymers. Based on the above founding, the motivation behind much of this activity has been provided by the prospect of generating, by deliberate design, a wide range of purpose-build materials with predetermined structures and useful properties of electric, magnetic, optical and catalytic, we try to conclude the main factors of influencing the synthesis of coordination polymers, find the regulating functions of organic ligands for structure, catch the synthesis rules. So we find a way by which we can get the organic-transition metal polymers with N- or O-Ligands generated with in situ acylation reaction.The coordination chemistry of the organic ligands H4bbh (= benzene-1, 2, 4, 5-bihydrazide) and H3bcbh (= benzene-4-carboxylate-1, 2-bihydrazide), which is generated through the in situ hydrothermal acylate reaction of benzene-1, 2, 4-tricarboxylate and benzene-1, 2, 4, 5-tetracarboxylate, respectively, and hydrazine hydrate, with inorganic cobalt salt has been investigated. Three new coordination polymers were prepared and fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The compound Co(μ3-H2bbh)(phen) (1) (triclinic, P-1; a = 9.762(4) ?, b = 10.169(4) ?, c = 11.143(4) ?, α= 80.96(3)?, β = 64.49(3)?, γ = 71.88(3)?, Z = 2) was synthesized from the reaction of CoCl2·6H2O, H4bta (= benzene-1,2,4,5-tetracarboxylic acid), N2H4·H2O, phen (= 1,10-phenanthroline) and H2O, and consists of one-dimensional double-chains that are linked to each other by weak noncovalent л-л stacking interaction into three-dimensional structure. Co(μ4-H2bbh)(H2O)2 (2) (monoclinic, P2(1)/c; a = 6.873(2) ?, b = 7.5962(14) ?, c = 10.046(2) ?, β = 95.281(16)?, Z = 2) was generated by the combination of CoCl2·6H2O, H4bta, N2H4·H2O and H2O. It adopts a three-dimensional structural motif in the solid state with channels consisted of 20-numbered rings (3.11×10.66 ?2 cross-section size). Co(μ3-Hbcbh)(bpy) (3) (monoclinic, Cc; a = 9.9464(13) ?, b = 23.685(5) ?, c = 7.9491 (16) ?, β = 117.677(13)?, Z = 4) was obtained from the mixture of CoCl2·6H2O, N2H4·H2O, H3btc (= benzene-1, 2, 4-tricarboxylate), bpy (=2,2′-dipyridyl) and H2O, and features two dimensional plane.Complexes 1 and 2 have intramolecular antiferromagnetic interaction.The hydrothermal reaction of CoCl2·6H2O, bdc(=benzene-1, 3-dicarboxylate), bpy(=2,2′-dipyridyl) and H2O produced the chain-like compound Co2(μ2-bdc)(μ3-bdc)(bpy)2(4) with two coordinating mode of μ2-BDC and μ3-BDC. The result has shown that the compound belongs to the triclinic P-1 space group with triclinic, P2(1)/c; a = 9.3384(14) ?, b = 11.272(3) ?, c = 16.769(4) ?, α= 98.705(14)°, β = 94.571(15)°, γ= 112.219(16)°, V = 1597.1(6) ?3, Z = 2. The crystal is stabilized by H-bonded 3-D network. The compound [Co2(bta)(bpy)2(H2O)]n (5) (orthorhombi, C222(1), a = 10.996(2) ?, b = 19.144(5) ?, c = 12.411(2) ?, α = 80.96(3)?, β = 64.49(3)?, γ = 71.88(3)?, V = 2612.6(10) ?3, Z = 8) was synthesized from the reaction of CoCl2·6H2O, H4bta (= benzene-1,2,4,5-tetracarboxylic acid), bpy, and H2O and features infinite two...
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