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首页> 外文期刊>Crystal growth & design >Construction of metal-organic frameworks (M = Cd(II), Co(II), Zn(II), and Cu(II)) based on semirigid oxadiazole bridging ligands by solution and hydrothermal reactions
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Construction of metal-organic frameworks (M = Cd(II), Co(II), Zn(II), and Cu(II)) based on semirigid oxadiazole bridging ligands by solution and hydrothermal reactions

机译：基于半刚性恶二唑桥联配体的溶液和水热反应构建金属有机骨架（M = Cd（II），Co（II），Zn（II）和Cu（II））

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摘要

Two new symmetric and unsymmetrical semirigid organic ligands 2,5-bis(4-(1H-1,2,4-triazol-1-ylmethyl)phenyl)-1,3,4-oxadiazole (L1) and 4-(1H-1,2,4-trizol-1-ylmethyl)benzoic acid (L2) have been prepared. L2 was generated from L1 by a hydrothermal reaction via the hydrolysis of the central oxadiazole ring of L1. The solution and hydrothermal reactions of L1 with various inorganic M(II) (M = Cd, Co, Zn, and Cu) ions have been investigated. Compounds [Cd(L1)(2)](NO3)(2) (1), [Cu(L1)(2)](NO3)(2) (2), and [Cu(L1)]Cl-2 center dot 2(H2O) (3) were obtained in solution by a combination of L1 with corresponding metal salts, while compounds Zn(L2)(2) (4), Co(L2)(2) (5), and [Co(L2)(2)]center dot H2O (6) were synthesized by a hydrothermal technique with in situ generated unsymmetrical L2 ligand. In addition, compounds 4-6 could also be prepared by direct combination of L2 with corresponding metal salts under the same hydrothermal conditions. All six new coordination polymers were fully characterized by infrared spectroscopy, elemental analysis, single-crystal X-ray diffraction, and thermogravimetric analysis. Compounds 1-3 are isostructural and feature a one-dimensional chain motif composed of an M2L2-macroring as the based building block. Compounds 4 and 5 form a novel chiral and acentric non-interpenetrating two-dimensional network consisting of right- and left-handed helical ML chains, respectively. Compound 6 adopts a unique non-interpenetrating three-dimensional framework, in which the inorganic center dot center dot center dot Co-O-Co-O center dot center dot center dot chains are connected to each other through unsymmetric L2 ligands. In the solid state, L1-L2 and their complexes 1-6 are luminescent. The Kurtz powder measurements show that both 4 and 5 are nonlinear optical (NLO) active and have potential applications as NLO-active materials.
机译：两个新的对称和非对称半刚性有机配体2,5-双（4-（1H-1,2,4-三唑-1-基甲基）苯基）-1,3,4-恶二唑（L1）和4-（1H-已经制备了1,2,4-三唑-1-基甲基）苯甲酸（L2）。 L2是通过L1的中心恶二唑环的水解通过水热反应从L1产生的。研究了L1与各种无机M（II）（M = Cd，Co，Zn和Cu）离子的溶液和水热反应。化合物[Cd（L1）（2）]（NO3）（2）（1），[Cu（L1）（2）]（NO3）（2）（2）和[Cu（L1）] Cl-2中心点1（H2O）（3）在溶液中通过L1与相应的金属盐的组合而获得，而化合物Zn（L2）（2）（4），Co（L2）（2）（5）和[Co（ L2）（2）]中心点H2O（6）是通过水热技术与原位生成的不对称L2配体合成的。另外，化合物4-6也可以通过在相同的水热条件下将L 2与相应的金属盐直接结合来制备。所有六种新的配位聚合物均通过红外光谱，元素分析，单晶X射线衍射和热重分析进行了全面表征。化合物1-3具有同构结构，并具有由M2L2宏组成的一维链基序作为基础结构单元。化合物4和5分别形成一个由右手和左手螺旋ML链组成的新型手性和无心非互穿二维网络。化合物6采用独特的不互穿的三维框架，其中无机中心点中心点中心点Co-O-Co-O中心点中心点中心点链通过不对称的L2配体相互连接。在固态下，L 1 -L 2及其配合物1-6是发光的。 Kurtz粉末测量结果表明4和5都是非线性光学（NLO）活性材料，具有作为NLO活性材料的潜在应用。

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