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首页> 外文期刊>Crystal growth & design >A unique example of structural diversity tuned by apparently innocent o -, m -, and p -nitro substituents of benzoate in their complexes of Mn(II) with 4,4′-bipyridine: 1D ladder, 2D sheet, and 3d framework
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A unique example of structural diversity tuned by apparently innocent o -, m -, and p -nitro substituents of benzoate in their complexes of Mn(II) with 4,4′-bipyridine: 1D ladder, 2D sheet, and 3d framework

机译：在Mn（II）与4,4'-联吡啶配合物中的苯甲酸酯的明显纯正的o-，m-和对硝基取代基调节的结构多样性的独特示例：1D阶梯，2D薄片和3d骨架

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Four new Mn(II) coordination polymers [Mn(4,4′-bpy)(C _6H_5COO)_2]_n (1), [Mn(4,4′-bpy) (o-(NO_2)C_6H_4COO)_2]_n (2), [Mn(4,4′-bpy)(m-(NO_2)C_6H_4COO) _2]_n (3), and [Mn(4,4′-bpy)(p-(NO_2)C _6H_4COO)_2]_n (4) (where 4,4′-bpy = 4,4′-bipyridine) have been synthesized by self-assembly of the primary ligands, benzoate and the o-, m-, and p-isomers of nitrobenzoates, respectively, together with 4,4′-bpy as the secondary spacer. All four complexes were characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction analyses, and variable-temperature magnetic measurements. The structural analyses reveal that complexes 1 and 3 are constructed by linear fused chains through double syn-syn (for 1) or syn-anti (for 3) carboxylate-bridged Mn(II), which are further linked to one another by trans coordinated 4,4′-bpy bridges, giving rise to a rectangular grid-like two-dimensional (2D) net. Complex 2 features one-dimensional (1D) molecular ladder formed by both syn-syn and syn-anti carboxylate-bridged dimeric Mn(II) units which are joined alternately by 4,4′-bpy. Complex 4 is formed by fused zigzag chains of double syn-syn carboxylate-bridged Mn(II) that are connected by cis oriented 4,4′-bpy to generate an unprecedented three-dimensional (3D) framework. The dimensionality of the complexes thus varies from 1D to 2D to 3D on changing the position of the nitro group from o- to m- to p- in the benzoate, showing explicitly the tuning ability of this apparently innocent substituent on the topology of the coordination polymer. Variable-temperature (1.8-300 K) magnetic susceptibility measurements showed the presence of antiferromagnetic coupling in all four complexes that have been fitted with an infinite classical-spin chain model derived by Fisher for 1, 3, and 4 (J = -0.779(2), -0.855(2), and -0.536(2) cm~(-1), respectively) and van Vleck equation for 2 (J = -0.354(2) cm~(-1)).
机译：四种新的Mn（II）配位聚合物[Mn（4,4'-bpy）（C _6H_5COO）_2] _n（1），[Mn（4,4'-bpy）（o-（NO_2）C_6H_4COO）_2] _n （2），[Mn（4,4'-bpy）（m-（NO_2）C_6H_4COO）_2] _n（3）和[Mn（4,4'-bpy）（p-（NO_2）C _6H_4COO）_2 ] _n（4）（其中4,4'-bpy = 4,4'-联吡啶）分别通过主要配体苯甲酸酯和硝基苯甲酸酯的邻，间和对异构体的自组装合成以及4,4'-bpy作为辅助间隔基。通过元素分析，红外光谱，单晶X射线衍射分析和可变温度磁测量来表征所有四个复合物。结构分析表明，配合物1和3是由线性稠合链通过双syn-syn（对于1）或syn-anti（对于3）由羧酸盐桥接的Mn（II）构成的，它们进一步通过反式配位相互连接4,4'-bpy桥，产生一个矩形网格状的二维（2D）网络。配合物2具有一维（1D）分子阶梯，该分子阶梯由顺式-顺式和顺式-抗羧酸盐桥联的二聚Mn（II）单元形成，它们通过4,4'-bpy交替连接。配合物4是由双顺式-顺式羧酸盐桥接的Mn（II）的锯齿形链形成的，它们通过顺式4,4'-bpy相连，生成了前所未有的三维（3D）骨架。因此，在将苯甲酸酯中的硝基位置从o-转变为m-转变为p-时，配合物的尺寸从1D到2D到3D不等，这清楚地表明了这种明显无害的取代基在配位拓扑上的调节能力。聚合物。可变温度（1.8-300 K）的磁化率测量表明，在所有四个配合物中均存在反铁磁耦合，这些配合物已被Fisher推导出的1、3和4的无限经典自旋链模型拟合（J = -0.779（ 2），-0.855（2）和-0.536（2）cm〜（-1））和2的van Vleck方程（J = -0.354（2）cm〜（-1））。

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