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Metal/Carboxylate-Induced Versatile Structures ofNine 0D → 3D Complexes with Different Fluorescent and ElectrochemicalBehaviors

机译:金属/羧酸盐诱导的通用结构九种具有不同荧光和电化学性质的0D→3D配合物行为举止

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摘要

To investigate the effect of the polycarboxylates and metal ions on the assembly and structures of complexes based on a thiophene-containing bis-pyridyl-bis-amide N,N′-bis(pyridine-3-yl)thiophene-2,5-dicarboxamide (3-bptpa) ligand, nine 0D → 3D complexes of [Ni2(3-bptpa)4(1,2-BDC)2(H2O)2] (>1), [Ni(3-bptpa)(IP)(H2O)2]·H2O (>2), [Ni(3-bptpa)(5-MIP)(H2O)2]·H2O (>3), [Ni(3-bptpa)(5-NIP)(H2O)] (>4), [Ni(3-bptpa)(5-AIP)]·2H2O (>5), [Ni2(OH)(3-bptpa)(1,3,5-BTC)]·DMA·5H2O (>6), [Cu(3-bptpa)(5-MIP)]·3H2O (>7), [Cu(3-bptpa)(5-AIP)(H2O)0.25]·H2O (>8), and [Cu(3-bptpa)(1,3,5-HBTC)] (>9) (1,2-H2BDC = 1,2-benzenedicarboxylic acid, H2IP = 1,3-benzenedicarboxylic acid, 5-H2MIP = 5-methylisophthalic acid, 5-H2NIP = 5-nitroisophthalic acid, 5-H2AIP = 5-aminoisophthalic acid, DMA = N,N′-dimethylacetamide, and 1,3,5-H3BTC = 1,3,5-benzenetricarboxylic acid) have been hydrothermally/solvothermally synthesized and structurally characterized by IR, thermogravimetric, powder X-ray diffraction, and single-crystal X-ray diffraction. Complex >1 is a zero-dimensional (0D) bimetallic complex. Complexes >2 and >3 feature two similar one-dimensional ladderlike structures. Complex >4 displays a two-dimensional (2D) 4-connected network based on single-metallic nodes. Complex >5 shows a 2D double-layer structure containing a pair of 63 [Ni(5-AIP)] honeycomblike sheets. Complex >6 is a 3,5-connected three-dimensional (3D) framework derived from bimetallic nodes and 63 [Ni2(OH)(1,3,5-BTC)] honeycomblike sheets. Complex >7 displays a 2D 4-connected grid based on bimetallic nodes. Complex >8 features a 2D double-layerstructure based on two 4-connected [Cu(3-bptpa)(5-AIP)] sheets andbridging coordinated water molecules. Complex >9 is a2D structure extended by incomplete deprotonation of 1,3,5-HBTC and3-bptpa linkers. The effect of the metal ions and polycarboxylateson the structures of the title complexes was discussed, and the fluorescentproperties of >1–>9 were investigated.The carbon paste electrodes bulk-modified by complexes >3, >5, and >6–>9 show differentelectrocatalytic activities for the oxidation of ascorbic acid aswell as the reduction of hydrogen peroxide, nitrites, and bromates.
机译:研究聚羧酸盐和金属离子对基于含噻吩的双吡啶基双酰胺N,N'-双(吡啶-3-基)噻吩-2,5-二甲苯酰胺的配合物的组装和结构的影响(3-bptpa)配体,[Ni2(3-bptpa)4(1,2-BDC)2(H2O)2](> 1 ),[Ni(3- bptpa)(IP)(H2O)2]·H2O(> 2 ),[Ni(3-bptpa)(5-MIP)(H2O)2]·H2O(> 3 ),[Ni(3-bptpa)(5-NIP)(H2O)](> 4 ),[Ni(3-bptpa)(5-AIP)]·2H2O(> 5 ),[Ni2(OH)(3-bptpa)(1,3,5-BTC)]·DMA·5H2O(> 6 ),[Cu(3-bptpa)(5 -MIP)]·3H2O(> 7 ),[Cu(3-bptpa)(5-AIP)(H 2 O) 0.25 ] ·H 2 O(> 8 )和[Cu(3-bptpa)(1,3,5-HBTC)](> 9 ) (1,2-H 2 BDC = 1,2-苯二甲酸,H 2 IP = 1,3-苯二甲酸,5-H 2 MIP = 5-甲基间苯二甲酸,5-H 2 NIP = 5-硝基间苯二甲酸,5-H 2 AIP = 5-氨基间苯二甲酸,已通过水热/溶剂热合成DMA = N,N'-二甲基乙酰胺和1,3,5-H 3 BTC = 1,3,5-苯三甲酸),并通过IR,热重,粉末X射线衍射和单晶X射线衍射。络合物> 1 是零维(0D)双金属络合物。复合体> 2 和> 3 具有两个相似的一维梯形结构。复合体> 4 显示基于单金属节点的二维(2D)4连接的网络。复数> 5 显示了一个二维双层结构,其中包含一对6 3 [Ni(5-AIP)]蜂窝状薄片。复杂> 6 是一个3,5-连接的三维(3D)框架,该框架源自双金属节点和6 3 [Ni 2 (OH) (1,3,5-BTC)]蜂窝状薄片。复杂> 7 显示基于双金属节点的2D 4连接网格。复杂的> 8 具有2D双层结构基于两个4个连接的[Cu(3-bptpa)(5-AIP)]图纸和桥接协调的水分子。复合体> 9 是一个1,3,5-HBTC的不完全质子化扩展了二维结构3-bptpa链接器。金属离子和聚羧酸盐的作用对标题配合物的结构进行了讨论,并且荧光研究了> 1 – > 9 的属性。由复合物> 3 ,> 5 和> 6 – > 9 批量修饰的碳糊电极显示不同抗坏血酸的电催化活性以及过氧化氢,亚硝酸盐和溴酸盐的还原。

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