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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Silver coordination polymers with tri- and hexacyanoethyl-functionalized macrocyclic ligands
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Silver coordination polymers with tri- and hexacyanoethyl-functionalized macrocyclic ligands

机译：具有三和六氰乙基功能化的大环配体的银配位聚合物

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摘要

Tri-and hexa-cyanoethyl functionalized 17-(L-1) and 42-membered (L-2) macrocyclic compounds were obtained by [1 + 1] (for L-1) or [2 + 2] (for L-2) cyclocondensation of the corresponding dialdehyde and diethylenetriamine, followed by hydrogenation by KBH4 and subsequent cyano-functionalization with acrylonitrile. They react with silver nitrate, leading to the formation of [AgL1](NO3) (1) and of the metalorganic coordination polymers [Ag-2(NO3)(2)L-1](n) (2) and {[Ag2L2](NO3)(2)}(n) (3). The complexes were characterized by elemental analysis, H-1 NMR, C-13 NMR, IR spectroscopies, and ESI-MS; moreover, L-2, 1, 2 and 3 were also characterized by single crystal X-ray diffraction. The metal cation in 1 is pentacoordinated with a N3O2 coordination environment; in 2, the metal cations display N4O2 octahedral and N2O3 square-pyramid coordination and in 3 they are in square-planar N-4 sites. In 1, the ligand acts as a pentadentate chelator, and in the other two cases, the ligands behave as octadentate chelators in a 1 kappa N-3:kappa O-2,2 kappa N,3 kappa N,4 kappa N (in 2) or 1 kappa N-3,2 kappa N-3,3 kappa N,4 kappa N fashion (in 3). The cyanoethyl strands of the ligands are directly involved in the formation of the 2D frameworks of 2 and 3, which in the former polymer can be viewed as a net composed of hexametallic 36-membered macrocyclic rings and in the latter generates extra hexametallic 58-membered cyclic sets that form zig-zag layers. The thermal analytical and electrochemical properties of these silver complexes were also studied.
机译：三和六氰乙基功能化的17-（L-1）和42元（L-2）大环化合物是通过[1 +1]（对于L-1）或[2 + 2]（对于L-2）获得的）将相应的二醛和二亚乙基三胺进行环缩合，然后用KBH4氢化，再用丙烯腈进行氰基官能化。它们与硝酸银反应，导致形成[AgL1]（NO3）（1）和金属有机配位聚合物[Ag-2（NO3）（2）L-1]（n）（2）和{[Ag2L2 ]（NO3）（2）}（n）（3）。通过元素分析，H-1 NMR，C-13 NMR，IR光谱和ESI-MS对配合物进行表征。此外，L-2、1、2和3还通过单晶X射线衍射表征。 1中的金属阳离子在N3O2配位环境中被五配位;在2中，金属阳离子显示N4O2八面体和N2O3方金字塔配位;在3中，它们在方形N-4位平面中。在1中，配体充当五齿螯合剂，在其他两种情况下，配体在1 kappa N-3：kappa O-2,2 kappa N，3 kappa N，4 kappa N（in 2）或1 kappa N-3，2 kappa N-3，3 kappa N，4 kappa N fashion（在3中）。配体的氰乙基链直接参与2和3的2D骨架的形成，在前者中可以将其视为由六金属36元大环组成的网，而在后者中则生成58元的六金属额外环形成锯齿形图层的循环集。还研究了这些银配合物的热分析和电化学性质。

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