Tuning of Valence States, Bonding Types, Hierarchical Structures, and Physical Properties in Copper/Halide/Isonicotinate System

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• 作者：Min-Min Liu ; Juan-Juan Hou ; Zhi-kai Qi ; Li鈭扤a Duan ; Wen-Juan Ji ; Cai-yun Han ; Xian-Ming Zhang
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：April 21, 2014
• 年：2014
• 卷：53
• 期：8
• 页码：4130-4143
• 全文大小：961K
• 年卷期：v.53,no.8(April 21, 2014)
• ISSN：1520-510X

文摘

Seven cupric halide coordination polymers, namely [Cu₅(OH)₃Br₃(ina)₄] (1), [Cu₅(OH)₃Cl₃(ina)₄] (2), [Cu₂(OH)Cl(ina)₂] (3), [Cu₃(OH)₂Cl₂(ina)₂]路2H₂O (4), [Cu₃(OH)₂Br₂(ina)₂]路2H₂O (5), [Cu₂Cl₂(ina)₂(H₂O)₂] (6), [Cu₂Cl(ina)₂(gca)(H₂O)] (7), cupric complex templated cuprous halide [Cu^II(Me-ina)₂(H₂O)][Cu^I₅Br₇] (8), and organic templated cuprous halide Me₂-ina[Cu₂Br₃] (9) (Hina = isonicotinic acid), were prepared from the starting materials of cupric halide and Hina via fine-tuning solvothermal reactions. According to valence states of copper, 1鈥?b>7 are copper(II) complexes, 8 is a mixed-valent Cu(I,II) complex, while 9 is a Cu(I) compound. According to bonding types of halides, nine complexes can be classified as three types: complexes 1鈥?b>3 include only normal X鈥揅u bond (X = halide); complexes 4鈥?b>7 include normal X鈥揅u bond and X路路路Cu weak bond; complexes 8 and 9 include normal X鈥揅u bond and X路路路H鈥揅 halogen hydrogen bonds. Complexes 1 and 2 are isomorphic three-dimensional (3D) pcu topological metal organic frameworks (MOFs) with butterfly-like Cu₄(渭₃-OH)₂X₂ and steplike Cu₆(渭₃-OH)₄ cores as nodes, showing strong ferromagnetic couplings. Complex 3 also is a pcu topological MOF with only butterfly-like Cu₄(渭₃-OH)₂Cl₂ clusters as nodes, presenting spin canting antiferromagnetic behavior. Isostructural 4 and 5 are Cu₃(OH)₂ clusters based two-dimensional (2D) (4,4) layers, which are extended into 3D eight-connected networks via weak Cu路路路X bonds, showing ferromagnetic coupling. Antiferromagnetic 6 is a simple one-dimensional coordination polymer, which is extended via weak Cu路路路Cl bonds into 3D (3,4)-connected networks. Paramagnetic 7 is a ladderlike polymer, which is extended into 2D (3,4)-connected layer via weak Cu路路路Cl bonds. The syntheses of polymeric cupric complexes 1鈥?b>7 mainly result from differences in reactant ratio and pH value. Utilization of reducing methanol generated novel cubane-containing [Cu₅Br₇]^{2鈥?/sup> chain templated by paddlewheel-like [CuII(Me-ina)₂]2+ 8 and face-shared dimer-containing [Cu₂Br₃]鈭?/sup> chain templated by N-methylated and O-esterificated Me₂-ina 9. Complex 9 exhibits a strong red emission and a weaker green emission upon excitation.}