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Fe(III) and Cu(II) coordination polymers assembled from di/tris-phosphonic acid and auxiliary ligands:Structure, SOD-like activity and magnetic behavior
Journal of Solid State Chemistry ( IF 3.2 ) Pub Date : 2018-07-18 , DOI: 10.1016/j.jssc.2018.07.008
Lu Feng , Hong Zhou , Hailong Xu , Wentao Huang , Tianyu Zeng

Hydrothermal reactions of (benzylazanediyl)bis(methylene)-diphosphonic acid (H4L1) or (benzene-1,3,5-triyltris(methylene))triphosphonic acid (H6L2) with Fe(III)/Cu(II) nitrate and 4, 4′-bipy or 2, 2′-bipy result in five new phosphonates, namely, [FeHL1(H2O)]n (1), {[Cu2L1(4, 4′-bipy)0.5(H2O)]·0.25H2O}n (2), [Cu2H2L2(4, 4′-bipy)(H2O)2]n (3), [CuH4L2(2, 2′-bipy)]n (4) and [Cu2(H4L2)2(2, 2′-bipy)2(H2O)4] (5), respectively. X-ray structural analysis indicates that 2 and 3 feature 3D framework structures with 3, 3, 3, 4-connected and 4, 5-connected topology; 1 and 4 display 1D chain structures, while 5 has a dimer structure. The di- or trisphosphonate ligands (H4L1 and H6L2) in the five complexes adopt different coordination modes and auxiliary ligands (4, 4′-bipy and 2, 2′-bipy) control the dimensionality of the final complexes. The superoxide dismutase (SOD) activities of 25 were assessed by modified nitrobluetetrazolium (NBT) assay. The IC50 values required to yield 50% inhibition of the reduction of NBT are 1.84, 2.02, 6.95 and 1.70 μM for 25, respectively, demonstrating better SOD-like activity than most of the Cu-SOD mimic enzymes reported in literatures. Among them, 2 and 3 have good stability and reusability under the simulative physiological conditions. The dismutation of 4 and 5 toward superoxide anion radicals can be attributed to the synergistic effect of the decomposition products of 4 and 5 containing Cu(II) and [H4L2]2- with or without 2, 2′-bipy or Cu(II) and 2, 2′-bipy, which were identified by liquid mass spectrometry (LC/MS). The magnetic properties of complexes 14 were also investigated, indicating the presence of magnetic exchange between metal ions. The results show that 1 and 3 exhibit antiferromagnetic interactions, while 2 and 4 show ferromagnetic interactions between metal centres.



中文翻译:

由二/三膦酸和辅助配体组装而成的Fe(III)和Cu(II)配位聚合物:结构,类SOD活性和磁行为

(苄基氮杂二基)双(亚甲基)-二膦酸(H 4 L 1)或(苯-1,3,5-三基三(亚甲基))三膦酸(H 6 L 2 )与Fe(III)/ Cu( II)硝酸盐和4,4'-联吡啶或2,2,'-联吡啶产生五个新的膦酸酯,即[FeHL 1(H 2 O)] n1),{[Cu 2 L 1(4,4' -bipy)0.5(H 2 O)]·0.25H 2 O} n2),[Cu 2 H 2 L 2(4,4'-bipy)(H 2 O)2 ] n3),[CuH 4 L 2(2,2' -bipy)] n4)和[Cu 2(H 4 L 22(2,2'-bipy)2(H 2 O)4 ](5)。X射线结构分析表明23具有3、3、3、4连接和4、5连接拓扑的3D框架结构。图14显示1D链结构,而5显示二聚体结构。二膦酸酯或三膦酸酯配体(H五个配合物中的4 L 1和H 6 L 2 )采用不同的配位方式,辅助配体(4、4'-bipy和2,2'-bipy)控制最终配合物的尺寸。通过改良的硝基蓝四唑(NBT)分析评估了25的超氧化物歧化酶(SOD)活性。抑制50%的NBT还原所需的IC 50值为25分别为1.84、2.02、6.95和1.70μM ,证明其比类文献中报道的大多数Cu-SOD模拟酶具有更好的SOD样活性。其中23在模拟生理条件下具有良好的稳定性和可重用性。的歧化45朝向超氧化物阴离子自由基可以归因于的分解产物的协同效应45含有Cu(II)和[H 4大号2 ] 2-有或没有2,2'-联吡啶或Cu (II)和2,2'-联吡啶,通过液相质谱(LC / MS)鉴定。复合物的磁特性1 - 4也进行了研究,表明金属离子之间的磁交换的存在。结果显示13表现出反铁磁相互作用,而24表现出金属中心之间的铁磁相互作用。

更新日期:2018-07-19
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