A Series of Cyanoacetato Copper(II) Coordination Polymers with Various N,N '-Ditopic Spacers: Structural Diversity, Supramolecular Robustness, and Magnetic Properties

Suvanvapee Porntiva; Boonmak Jaursup; Klongdee Fatima; Pakawatchai Chaveng; Moubaraki Boujemaa; Murray Keith S.; Youngme Sujittra

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A Series of Cyanoacetato Copper(II) Coordination Polymers with Various N,N '-Ditopic Spacers: Structural Diversity, Supramolecular Robustness, and Magnetic Properties

机译：一系列具有各种N，N'-异位间隔基的氰基乙酸铜（II）配位聚合物：结构多样性，超分子鲁棒性和磁性

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Five novel copper(II) coordination polymers containing cyanoacetate (cna) anion with various N,N'-ditopic spacers [Cu(cna)(2)(pyz)](n) (1), [Cu(cna)2(bpy)(H2O)(2)](n) (2), [Cu(cna)(2)(dpe)](n) (3), [Cu(cna)(2)(dpe)](n)(H2O)(n) (4), and [Cu(cna)(2)(bpa)](n) (5) (when pyz = pyrazine, bpy = 4,4'-bipyridyl, dpe = 1,2-di(4-pyridyl)ethylene, and bpa = 1,2-di(4-pyridyl)ethane) were structurally and spectroscopically characterized. Compound 1 shows a two-dimensional (2D) sheet structure constructed from mu(2)-1,3(syn,anti) coordinative mode of cyanoacetate and mu(2)-pyz linking adjacent Cu(II) centers. Compound 2 exhibits a one-dimensional (1D) polymeric chain which is formed by mu(2)-bpy bridging between [Cu(cna)(2)(H2O)(2)] units, whereas compounds 3-5 reveal 1D ladder-like structures which are built from double-mu(2)-dpe/bpa spacers connecting neighboring Cu(II) cyanoacetate dimers. Weak interactions such as hydrogen bonding and N...p and/or CH...pi interactions join the adjacent layers of 1 or polymeric chains of 2-5 to stabilize overall supramolecular networks. The thermal stabilities of 1-5 were investigated. Interestingly, compound 2 reveals a robust supramolecular framework constructed by 1D polymeric chains during thermal dehydration and rehydration processes, which has been further verified by spectroscopic techniques, elemental analyses, thermogravimetric analysis, and X-ray powder diffraction. Moreover, this behavior is not observed in the isomorphous series containing Co(II) and Ni(II) ions. The magnetic properties of 1 and 3 exhibit very weak antiferromagnetic interactions between Cu(II) centers.

机译：五种新颖的铜（II）配位聚合物，其中含有氰基乙酸根（cna）阴离子和各种N，N'-二位间隔基[Cu（cna）（2）（pyz）]（n）（1），[Cu（cna）2（bpy））（H2O）（2）]（n）（2），[Cu（cna）（2）（dpe）]（n）（3），[Cu（cna）（2）（dpe）]（n）（ H2O）（n）（4）和[Cu（cna）（2）（bpa）]（n）（5）（当pyz =吡嗪，bpy = 4,4'-联吡啶，dpe = 1,2-di （4-吡啶基）乙烯和bpa = 1,2-二（4-吡啶基）乙烷）的结构和光谱特征。化合物1显示二维（2D）片状结构，由氰基乙酸盐的mu（2）-1,3（syn，anti）配位模式和连接相邻Cu（II）中心的mu（2）-pyz构成。化合物2表现出一维（1D）聚合物链，该链由[Cu（cna）（2）（H2O）（2）]单元之间的mu（2）-bpy桥接形成，而化合物3-5显示一维梯形-由双mu（2）-dpe / bpa间隔基连接相邻的氰基乙酸铜Cu（II）二聚体构建的类似结构。弱相互作用（例如氢键和N ... p和/或CH ... pi相互作用）将1的相邻层或2-5的聚合物链连接在一起，以稳定整个超分子网络。研究了1-5的热稳定性。有趣的是，化合物2揭示了由一维聚合物链在热脱水和复水过程中构建的坚固的超分子骨架，该骨架已通过光谱技术，元素分析，热重分析和X射线粉末衍射进一步证实。此外，在包含Co（II）和Ni（II）离子的同构系列中未观察到此行为。 1和3的磁性能在Cu（II）中心之间表现出非常弱的反铁磁相互作用。

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《Crystal growth & design》 |2015年第8期|共9页
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Suvanvapee Porntiva; Boonmak Jaursup; Klongdee Fatima; Pakawatchai Chaveng; Moubaraki Boujemaa; Murray Keith S.; Youngme Sujittra;
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A Series of Cyanoacetato Copper(II) Coordination Polymers with Various N,N '-Ditopic Spacers: Structural Diversity, Supramolecular Robustness, and Magnetic Properties

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