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pH-dependent assembly of supramolecular architectures from 0D to 2D networks

机译：从0D到2D网络的超分子体系结构的pH依赖组装

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摘要

Five Cu(II)ibenzoate/4,4'-bipy complexes, namely, [Cu(H2O)(benzoate)2(4,4'-bipy)2](benzoic acid)2 center dot(4,4'-bipy) (1), [Cu-2(H2O)(2)(benzoate)(4)(4,4'-bipy)(3)]center dot(H2O)(9) (2), [Cu-2(benzoate)(4)(4,4'-bipy)(3)] (3), [Cu-3(H2O)(4)(benzoate)(6)(4,4'-bipy)(4.5)]center dot(4,4'-bipy) (H2O)(5) (4), and [Cu-3(OH)(2)(H2O)(2)(benzoate)(4)(4,4'-bipy)(2)] (5) (4,4'-bipy = 4,4'-bipyridine), have been synthesized through hydrothermal reaction of copper(II) nitrate, benzoic acid, and 4,4'-bipyridine under different pH conditions. The diverse product structures show the marked sensitivity of the structural chemistry of the aromatic carboxylate ligand to synthesis conditions. Complex 1, which exhibits a zero-dimensional (0D) structure of mononuclear copper(II), is formed at pH = 5.5. At pH = 6.0, dimeric copper(II) complexes of 2 and 3 are formed. Reaction at pH = 7 leads to a one-dimensional (11)) structure of 4. A further increase of the pH to 8.0 results in a two-dimensional (2D) structure of 5. Crystal data are monoclinic, space group P2, a = 13.992(4) angstrom, b = 5.7153(14) angstrom, c = 31.126(8) angstrom, beta = 100.513(5)degrees, Z = 2 for 1, monoclinic, space group C2/c, a = 30.283(5) angstrom, b = 15.139(2) angstrom = 14.457(2) angstrom, beta = 112.776(3)degrees, Z = 4 for 2, monoclinic, space group P2(1)/c, a = 5.8317(12) angstrom, b = 21.157(4) angstrom, c = 20.679(4) angstrom , beta = 94.343(3)degrees, Z = 2 for 3, triclinic, space group P (1) over bar, a = 14.016(3) angstrom, b = 18.492(4) angstrom, c = 19.353(4) angstrom, alpha = 66.220(3)degrees, beta = 79.948(4)degrees, gamma = 88.390(3)degrees, Z = 2 for 4, and monoclinic, space group P2(1)/c, a = 5.6880(16) angstrom, b = 17.917(5) angstrom, c 20.904(6) angstrom, beta = 92.959(5)degrees, Z = 2 for 5.
机译：五个Cu（II）ibenzoate / 4,4'-bipy络合物，即[Cu（H2O）（苯甲酸酯）2（4,4'-bipy）2]（苯甲酸）2中心点（4,4'-bipy ）（1），[Cu-2（H2O）（2）（苯甲酸酯）（4）（4,4'-联吡啶）（3）]中心点（H2O）（9）（2），[Cu-2（苯甲酸酯）（4）（4,4'-bipy）（3）]（3），[Cu-3（H2O）（4）（苯甲酸酯）（6）（4,4'-bipy）（4.5）]中心点（4,4'-bipy）（H2O）（5）（4）和[Cu-3（OH）（2）（H2O）（2）（苯甲酸酯）（4）（4,4'-bipy） （2）]（5）（4,4'-联吡啶= 4,4'-联吡啶），是通过硝酸铜（II），苯甲酸和4,4'-联吡啶在不同pH条件下的水热反应合成的。多样的产物结构显示出芳族羧酸酯配体的结构化学对合成条件的显着敏感性。在pH = 5.5时形成具有单核铜（II）的零维（0D）结构的配合物1。在pH = 6.0时，形成2和3的二聚铜（II）配合物。 pH = 7时的反应将导致4的一维（11）结构。将pH值进一步提高至8.0将导致二维（2D）结构为5。晶体数据为单斜晶系，空间群P2 / n ，a = 13.992（4）埃，b = 5.7153（14）埃，c = 31.126（8）埃，贝塔= 100.513（5）度，Z = 2，对于1，单斜，空间群C2 / c，a = 30.283 （5）埃，b = 15.139（2）埃= 14.457（2）埃，beta = 112.776（3）度，Z = 4（对于2），单斜，空间群P2（1）/ c，a = 5.8317（12）埃，b = 21.157（4）埃，c = 20.679（4）埃，beta = 94.343（3）度，Z = 2（3），三斜度，空间组P（1）在条上，a = 14.016（3）埃，b = 18.492（4）埃，c = 19.353（4）埃，alpha = 66.220（3）度，beta = 79.948（4）度，γ= 88.390（3）度，Z = 2为4，单斜，空间组P2（1）/ c，a = 5.6880（16）埃，b = 17.917（5）埃，c 20.904（6）埃，beta = 92.959（5）度，Z = 2 for 5。

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