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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Assembly and properties of transition-metal coordination polymers based on semi-rigid bis-pyridyl-bis-amide ligand: Effect of polycarboxylates on the dimensionality
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Assembly and properties of transition-metal coordination polymers based on semi-rigid bis-pyridyl-bis-amide ligand: Effect of polycarboxylates on the dimensionality

机译：基于半刚性双吡啶基双酰胺配体的过渡金属配位聚合物的组装和性能：聚羧酸盐对尺寸的影响

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Seven new coordination polymers, [Co(3-bpcd)(1,3-BDC)(H _2O) _3]·H _2O (1), [Co(3-bpcd)(1,2-BDC)(H _2O)]·H _2O (2), [Co _3(3-bpcd)(1,2,4-BTC) _2(H _2O) _4]·4H _2O (3), [Co(3-bpcd)(NPH)]·2H _2O (4), [Cu(3-bpcd)(1,3-BDC)] (5), [Cu(3-bpcd)(1,2-BDC)] (6), [Cu(3-bpcd)(1,3,5-HBTC)(H _2O)] _2·2H _2O (7) (3-bpcd = N,N′-bis(pyridin-3-yl) cyclohexane-1,4-dicarboxamide, 1,3-H _2BDC = 1,3-benzenedicarboxylic acid, 1,2-H _2BDC = 1,2-benzenedicarboxylic acid, 1,2,4-H _3BTC = 1,2,4-benzenetricarboxylic acid, H _2NPH = 3-nitrophthalic acid and 1,3,5-H _3BTC = 1,3,5-benzenetricarboxylic acid) have been hydrothermally synthesized by assembling transition-metal cobalt-copper salts with semi-rigid bis-pyridyl-bis-amide ligand 3-bpcd and different aromatic polycarboxylic acids. Complex 1 exhibits a one-dimensional (1D) sinusoidal-like chain, which is further assembled into a three-dimensional (3D) supramolecular framework through hydrogen-bonding interactions. Complex 2 possesses a 3D framework with 4-connected 6 ~6 topology, which contains a two-dimensional (2D) distorted asymmetric hexagonal grid. When 1,2,4-BTC is used in complex 3, a 3D framework with (6 ~3·8 ~2·10) _2(6 ~5·8) _2(8) topology is constructed. Complex 4 possesses a 3D framework with 4-connected 6 ~6 topology, which is similar to that of 2 except for containing a 2D symmetric hexagonal grid. When Co ~II ion is replaced by Cu ~II ion, the 3D framework of complex 5 with (4·6 ~2)(4·6 ~6·8 ~3) topology based on 3-bpcd and 1,3-BDC ligands is obtained. Complex 6 shows a 2D cross network consisting of a superposed Cu-3-bpcd 1D chain and 1,2-BDC, which is further expanded into a 3D supramolecular framework by hydrogen-bonding interactions. In complex 7, 1,3,5-HBTC is employed as the auxiliary ligand, and a 3D supramolecular framework based on the undulated 2D layers is formed through π-π stacking and hydrogen-bonding interactions. Both the metal ions and polycarboxylates play important roles in the construction of the title complexes. In addition, the electrochemical behaviors and the fluorescence properties of the seven complexes have been investigated.
机译：七个新的配位聚合物，[Co（3-bpcd）（1,3-BDC）（H _2O）_3]·H _2O（1），[Co（3-bpcd）（1,2-BDC）（H _2O） ]·H _2O（2），[Co _3（3-bpcd）（1,2,4-BTC）_2（H _2O）_4]·4H _2O（3），[Co（3-bpcd）（NPH）] ·2H _2O（4），[Cu（3-bpcd）（1,3-BDC）]（5），[Cu（3-bpcd）（1,2-BDC）]（6），[Cu（3- bpcd）（1,3,5-HBTC）（H _2O）] _2·2H _2O（7）（3-bpcd = N，N'-双（吡啶-3-基）环己烷-1,4-二甲酰胺，1 ，3-H _2BDC = 1,3-苯二甲酸，1,2-H _2BDC = 1,2-苯二甲酸，1,2,4-H _3BTC = 1,2,4-苯三甲酸，H _2NPH = 3-通过将过渡金属钴-铜盐与半刚性的双吡啶基-双酰胺配体3-bpcd和不同的芳族多元羧酸。配合物1表现出一维（1D）正弦状链，通过氢键相互作用进一步组装成三维（3D）超分子框架。复合体2具有3D框架，具有4个连接的6〜6拓扑，其中包含一个二维（2D）扭曲的不对称六边形网格。当在复合物3中使用1,2,4-BTC时，将构建具有（6〜3·8〜2·10）_2（6〜5·8）_2（8）拓扑的3D框架。复合体4具有3D框架，该框架具有4个连接的6〜6拓扑，该拓扑类似于2的拓扑，除了包含2D对称六边形网格。当Co〜II离子替换为Cu〜II离子时，基于3-bpcd和1,3-BDC的具有（4·6〜2）（4·6〜6·8〜3）拓扑的配合物5的3D框架获得配体。配合物6显示了一个2D交叉网络，该网络由一个重叠的Cu-3-bpcd 1D链和1,2-BDC组成，并通过氢键相互作用进一步扩展为3D超分子框架。在复合物7、1,3,5-HBTC中用作辅助配体，并通过π-π堆积和氢键相互作用形成了基于起伏2D层的3D超分子骨架。金属离子和聚羧酸盐在标题配合物的构建中均起重要作用。此外，已经研究了七个配合物的电化学行为和荧光性质。

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