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Ligand-directed and pH-controlled assembly of chiral 3d-3d heterometallic metal-organic frameworks

机译:手性3d-3d杂金属金属-有机骨架的配体导向和pH控制组装

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摘要

Use of unsymmetric ligand 1,2,4-benzenetricarboxylic acid (1,2,4-H _3BTC) and controlling the reaction pH value enabled isolation of two novel chiral 3d-3d heterometallic complexes [Zn_2Co(tib) _3(H_2O)_5][Zn_6(tib) _2(1,2,4-BTC)_6]·12.7H_2O (1) and [ZnCo(tib)(1,2,4-BTC)(H_2O)_2]Cl·3H_2O (2) [tib =1,3,5-tris(1-imidazolyl)benzene]. Comparative study revealed that the use of symmetric ligand 1,3,5-benzenetricarboxylic acid (1,3,5-H_3BTC) resulted one achiral 3d-3d heterometallic complex [ZnCo(tib)(1,3,5-BTC)Cl] (3) with 3D structure. Complex 1 is a 2D network with cationic and anionic layers arranged alternately, while 2 is a 3D framework with rare 1D helical water chains. Furthermore, complex 1 displays ferroelectric behavior with a remnant electric polarization (P_r) of ~0.177 μC/cm~2 and an electric coercive field (E_c) of ~17.68 kV/cm.
机译:使用不对称配体1,2,4-苯三羧酸(1,2,4-H _3BTC)并控制反应pH值可分离出两种新型手性3d-3d杂金属配合物[Zn_2Co(tib)_3(H_2O)_5] [Zn_6(tib)_2(1,2,4-BTC)_6]·12.7H_2O(1)和[ZnCo(tib)(1,2,4-BTC)(H_2O)_2] Cl·3H_2O(2)[ tib = 1,3,5-三(1-咪唑基)苯]。对比研究表明,使用对称配体1,3,5-苯三羧酸(1,3,5-H_3BTC)生成了一种非手性3d-3d杂金属配合物[ZnCo(tib)(1,3,5-BTC)Cl] (3)具有3D结构。配合物1是具有交替排列的阳离子和阴离子层的2D网络,而配合物2是具有稀有的1D螺旋水链的3D框架。此外,配合物1的铁电行为具有约0.177μC/ cm〜2的残余极化强度(P_r)和约17.76 kV / cm的矫顽电场(E_c)。

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