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首页> 外文期刊>Crystal growth & design >Synthesis, magnetic properties, and structural investigation of mixed-ligand Cu(II) helical coordination polymers with an amino acid backbone and N-donor propping: 1-D helical, 2-D hexagonal net (HCB), and 3-D ins topologies
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Synthesis, magnetic properties, and structural investigation of mixed-ligand Cu(II) helical coordination polymers with an amino acid backbone and N-donor propping: 1-D helical, 2-D hexagonal net (HCB), and 3-D ins topologies

机译：具有氨基酸主链和N-供体支撑的混合配体Cu（II）螺旋配位聚合物的合成，磁性和结构研究：1-D螺旋，2-D六角网（HCB）和3-D ins拓扑

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Three Cu(II) coordination polymers, {[Cu-(L-cysteate)(1,4-Bix)(H _2O)]-H_2O}_n (1), {[Cu(L-aspartate)-(1,4-Bix) _(0.5)]-H_2O}n (2), and {[Cu(L-aspartate)(4,4'-Bpy) _(0.5)] H_2O}_n (3), have been synthesized solvothermally, employing enantiopure L-amino acids and bidentate N-donor ligands, 1,4-bis(imidazol-1-ylmethyl)benzene (1,4-Bix) and 4,4'-bipyridyl-(4,4'- Bpy), to yield 1-D, 2-D, and 3-D helical coordination polymers, respectively. All the three neutral frameworks are well-characterized by various physicochemical methods (C,H,N analysis, IR, TGA) including the single crystal X-ray diffraction technique. The chiral nature of complexes 2 and 3 was established using solid state CD spectra. Structural investigation of complex 1 revealed 1-D helical chains, whereas that of complex 2 confirms a chiral and helical two-dimensional 63-hcb net, with helicity propagating in both the dimensions. Cu(II) nodes with the mixed ligands in complex 3 generate a three-dimensional framework by the pillaring of Cu(L-aspartate) 2-D helical layers by 4,4-Bpy units, identified as a (3,4)-coordinated binodal net with (6~3)(6~5.8)-ins topology. The temperature-dependent magnetic properties of the L-aspartic acid derived for complexes 2 and 3 were studied in detail. Complex 2 showed weak antiferromagnetic behavior, which matches well with the crystallographic parameters (syn-anti conformation of carboxylate bridged Cu(II), with lowest Cu-Cu distance 5.367 ?). Similarly, complex 3, with a shorter and rigid N-donor ligand, 4,4'-Bpy, and the carboxylate group of the amino acid moiety linking the adjacent metal centers in the syn-anti conformation, also displayed a weak antiferromagnetic behavior at lower temperatures, showing the weak exchange couplings between Cu(II) centers.
机译：三种Cu（II）配位聚合物，{[Cu-（L-半胱氨酸）（1,4-Bix）（H _2O）]-H_2O} _n（1），{[Cu（L-半胱氨酸）-（1,4 -Bix）_（0.5）]-H_2O} n（2）和{[Cu（L-天冬氨酸）（4,4'-Bpy）_（0.5）] H_2O} _n（3）溶剂热合成，使用对映体纯的L-氨基酸和双齿N-供体配体，1,4-双（咪唑-1-基甲基）苯（1,4-Bix）和4,4'-联吡啶基-（4,4'- Bpy），分别产生1-D，2-D和3-D螺旋配位聚合物。这三个中性骨架均通过包括单晶X射线衍射技术在内的各种物理化学方法（C，H，N分析，IR，TGA）得到了很好的表征。配合物2和3的手性是使用固态CD光谱确定的。配合物1的结构研究显示了1-D螺旋链，而配合物2的结构研究证实了手性和螺旋的二维63-hcb网，并且在两个维度上均具有螺旋性。配合物3中具有混合配体的Cu（II）节点通过以4,3-Bpy单元标记为Cu（L-天门冬氨酸）2-D螺旋层而形成三维框架，标识为（3,4）-具有（6〜3）（6〜5.8）-ins拓扑的协调二元网络。详细研究了配合物2和3衍生的L-天冬氨酸的温度相关磁性。配合物2显示出弱的反铁磁行为，这与晶体学参数（羧酸盐桥接的Cu（II）的顺-反构象，具有最低的Cu-Cu距离为5.367Ω）很好地匹配。类似地，具有较短且刚性的N-供体配体4,4'-Bpy和在顺-反构象中连接相邻金属中心的氨基酸部分的羧酸盐基团的配合物3也显示出弱的反铁磁行为。较低的温度，表明Cu（II）中心之间的交换耦合较弱。

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