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首页> 外文期刊>Crystal growth & design >Metal-Dependent Structural Variations and the Peculiarities of Hydrogen-Bonded Networks in the Highly Hydrated Copper(II), Nickel(II), and Palladium(II) Complexes of Bis-Dioxocyclam
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Metal-Dependent Structural Variations and the Peculiarities of Hydrogen-Bonded Networks in the Highly Hydrated Copper(II), Nickel(II), and Palladium(II) Complexes of Bis-Dioxocyclam

机译：Bis-Dioxocyclam高水合铜（II），镍（II）和钯（II）配合物中金属相关的结构变异和氢键网络的特殊性

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The crystal structures of the copper(II) (Cu2L14B.9H(2)O and Cu2L14B.12H(2)O), nickel(II) (Ni2L(14B).12H(2)O) and palladium(II) (Pd2L(14B).12H(2)O) complexes of the CC linked bis-dioxocyclam ligand have been determined by single crystal X-ray diffraction (bis-dioxocyclam, H4L14B = 6,6'-bi-(1,4,8,11-tetraazacyclotetradecane)-5,5',7,7'-tetraone). The planar coordination environment of the metal(II) ions is formed by cis-2N(amide) + cis-2N(amine) donor atoms. Additionally, the apical site in the copper(II) complexes is occupied by the water molecule. All complex molecules adopt a stretched conformation with intramolecular metal-metal distances ranging from 6.608 to 7.002 angstrom. The conformations of the macrocyclic subunits in M2L(14B) reveal considerable variations depending on the metal ion and differ significantly from those of the corresponding mono-macrocyclic dioxocyclam complexes ML14M (dioxocyclam, H2L14M = 1,4,8,11-tetraazacyclotetradecane-5,7-dione), thus resembling the behavior for the open-chain analogues. A detailed analysis of the 1H NMR spectra of the diamagnetic nickel(II) and palladium(II) complexes supports preservation of the conformational differences in aqueous solution. Electronic absorption spectra and electrochemical characteristics of the M2L14B complexes are also briefly discussed. Being highly hydrated solids, the bis-macrocyclic compounds are characterized by extended networks of hydrogen bonds. The water molecules form infinite aggregates differing by the structure and dimensionality - one-dimensional chains for Cu2L14B.9H(2)O, two-dimensional layers for Cu2L14B.12H(2)O and Ni2L14B.12H(2)O, and a three-dimensional network for Pd2L14B.12H(2)O.
机译：铜（II）（Cu2L14B.9H（2）O和Cu2L14B.12H（2）O），镍（II）（Ni2L（14B）.12H（2）O）和钯（II）（Pd2L）的晶体结构（14B）.CC连接的双-二氧杂环丁烷配体的（12B）.12H（2）O）络合物已通过单晶X射线衍射确定（双-二氧杂环丁烷，H4L14B = 6,6'-bi-（1,4,8， 11-四氮环十四烷）-5,5'，7,7'-四酮）。金属（II）离子的平面配位环境由顺式2N（酰胺）+顺式2N（胺）供体原子形成。另外，铜（II）配合物中的顶端位点被水分子占据。所有复杂分子均采用拉伸构象，分子内金属与金属的距离范围为6.608至7.002埃。 M2L（14B）中大环亚基的构象显示出很大的变化，具体取决于金属离子，并且与相应的单-大环二氧杂环丁烷配合物ML14M的构象显着不同（二氧杂环丁烷，H2L14M = 1,4,8,11-四氮杂环十四烷-5， 7-dione），因此类似于开链类似物的行为。对抗磁性镍（II）和钯（II）配合物的1H NMR光谱进行详细分析，有助于保留水溶液中的构象差异。还简要讨论了M2L14B配合物的电子吸收光谱和电化学特性。双大环化合物是高度水合的固体，其特征在于氢键的扩展网络。水分子形成无限的聚集体，其结构和尺寸各不相同-Cu2L14B.9H（2）O的一维链，Cu2L14B.12H（2）O和Ni2L14B.12H（2）O的二维层以及三个Pd2L14B.12H（2）O的三维网络。

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