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首页> 外文期刊>Crystal growth & design >Coordination polymers of 1,3,5-Tris(triazol-1-ylmethyl)-2,4,6- trimethylbenzene: Synthesis, structure, reversible hydration, encapsulation, and catalysis oxidation of diphenylcarbonohydrazide
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Coordination polymers of 1,3,5-Tris(triazol-1-ylmethyl)-2,4,6- trimethylbenzene: Synthesis, structure, reversible hydration, encapsulation, and catalysis oxidation of diphenylcarbonohydrazide

机译：1,3,5-三（三唑-1-基甲基）-2,4,6-三甲基苯的配位聚合物：二苯碳酰肼的合成，结构，可逆水合，包封和催化氧化

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Eight coordination polymers {[Co_3(L)_2(H _2O)_6Cl_6]·4H_2O}n (1), {[Co(L)_2Cl_2]·13H_2O}_n (2), {[Cu_3(L)_2(H_2O)_6Cl _6]·4H_2O}_n (3), {[Cu(L) _2Cl_2]·12H_2O}_n (4), {[Zn(L)_2(H_2O)_2](NO_3) _2·4H_2O}_n (5), {[Zn(L)_2(H _2O)_2](PF_6)_2·6H _2O}_n (6), {[ZnL(mal)] ·3H_2O}_n (7), and {[Zn_3(L)_2(fum)3(H_2O) _6]·2H_2O}_n (8) were synthesized by reactions of the flexible tripodal ligand 1,3,5-tris(triazol-1-ylmethyl)-2,4,6- trimethylbenzene (L) and/or fumaric acid (H2fum)/malonic acid (H _2mal), with corresponding metal salts, respectively. The structures of these polymers were established by elemental analysis, IR, powder and single-crystal X-ray diffraction analysis. Complexes 1 and 3 had an infinite two-dimensional (2D) honeycomb network. L as a cis-tridentate ligand coordinated to metal ions up and down alternatively. Complexes 2 and 4 possessed a one-dimensional (1D) chain hinged structure. L was a cis-bidentate ligand. Complexes 5 and 6 had a 2D network structure with (4,4) topology. L was a trans-bidentate ligand in 5, while in 6, L adopted a cis-configuration coordinated to metal ion bidentately. Complex 7 had a wavy 2D structure. L adopted a trans-configuration coordinated ion in the c-direction, while the malonate anion coordinated to metal ions in the b-direction in left- and right-helix alternatively. Complex 8 had an unusual 2D to three-dimensional (3D) interpenetration network structure. L was in trans-configuration coordinated to metal ions tridentately in the bc plane to form a ladder structure, and fumarate anion bridged the ladder in the a-axis to form a porous 2D coordination polymer. Adjacent 2D coordination polymers penetrated each other in the c-direction to form a 3D coordination with void dimensions consisting of 11 ? rhombic channels. The structures of 1 and 2 (or 3 and 4) indicate ligand/metal ratios had a significant influence on the structures of coordination polymers. The distinct structures of all these complexes demonstrated that the counteranions played an important role in the construction of coordination polymers. The isostructure between complexes 1 and 3, 2 and 4, and 5 indicate that the metal centers did not affect the structure of the complexes. Complex 8 with the characteristic of hydrophilic carboxylate groups and hydrophobic L was capable of absorbing water reversibly under 50 °C and encapsulating guest molecules, such as curcumin, diphenylcarbonohydrazide, and phenylfluorone, to form {(guest molecule)_x ? 8}_n. (where x = 0.2-0.4). The encapsulation behavior of 8 had been studied by elemental analysis, IR, thermogravimetric analysis (TG), and X-ray powder diffraction patterns (PXRD). Complex 8 could heterogeneously catalyze the oxidation of diphenylcarbonohydrazide in the presence of H_2O _2 in ethanol effectively. The oxidation process was facile, efficient, and environmental friendly.
机译：八种配位聚合物{[Co_3（L）_2（H _2O）_6Cl_6]·4H_2O} n（1），{[Co（L）_2Cl_2]·13H_2O} _n（2），{[Cu_3（L）_2（H_2O） _6Cl _6]·4H_2O} _n（3），{[Cu（L）_2Cl_2]·12H_2O} _n（4），{[Zn（L）_2（H_2O）_2]（NO_3）_2·4H_2O} _n（5） ，{[Zn（L）_2（H _2O）_2]（PF_6）_2·6H _2O} _n（6），{[ZnL（mal）]·3H_2O} _n（7）和{[Zn_3（L）_2 （fum）3（H_2O）_6]·2H_2O} _n（8）是通过柔性三脚架配体1,3,5-三（三唑-1-基甲基）-2,4,6-三甲基苯（L）反应合成的和/或富马酸（H2fum）/丙二酸（H _2mal），分别带有相应的金属盐。这些聚合物的结构通过元素分析，IR，粉末和单晶X射线衍射分析确定。配合物1和3具有无限的二维（2D）蜂窝网络。 L为顺式-三齿配体，可与金属离子交替上下配合。配合物2和4具有一维（1D）链铰链结构。 L是顺式-双齿配体。配合物5和6具有带有（4,4）拓扑的2D网络结构。 L在5中是反双齿配体，而在6中，L采用顺式构型与金属离子双齿配位。 Complex 7具有波浪形的2D结构。 L采用在c方向上的反式构型配位离子，而丙二酸根阴离子在b方向上在左螺旋和右螺旋中配位为金属离子。复合体8具有不寻常的2D到三维（3D）互穿网络结构。 L处于反式构型，在bc平面中与金属离子三齿配位以形成梯形结构，而富马酸酯阴离子在a轴上桥接了梯形，形成了多孔2D配位聚合物。相邻的2D配位聚合物在c方向上互相渗透，形成3D配位，其空隙尺寸由11？菱形通道。 1和2（或3和4）的结构表明配体/金属比对配位聚合物的结构有重大影响。所有这些配合物的独特结构表明，抗衡阴离子在配位聚合物的构建中起着重要作用。配合物1、3、2、4和5之间的同构结构表明金属中心不影响配合物的结构。具有亲水性羧酸盐基团和疏水性L的特征的配合物8能够在50℃下可逆地吸收水并且包封姜黄素，二苯基碳酰肼和苯基芴酮等客体分子，形成{（客体分子） 8} _n。 （其中x = 0.2-0.4）。通过元素分析，红外，热重分析（TG）和X射线粉末衍射图谱（PXRD）研究了8的封装行为。在乙醇中存在H_2O _2时，配合物8可以多相催化二苯碳酰肼的氧化。氧化过程简便，高效且环境友好。

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