Study on Imidazolate-Bridged Divalent Copper Ion Complexes Capped with Tris(1-pyrazolyl)methane
Study on Imidazolate-Bridged Divalent Copper Ion Complexes Capped with Tris(1-pyrazolyl)methane
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三(1-吡唑基)甲烷封端咪唑桥二价铜离子配合物的研究
DOI：
10.1016/j.poly.2017.03.045
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发表时间：
2017
期刊：
影响因子：
2.6
通讯作者：
and T. Ishida
中科院分区：
文献类型：
--
作者：
T. Kogane;A. Ondo;M. Yamasaki;T. Kanetomo;and T. Ishida
合成了四种以三(1-吡唑基)甲烷(Pz3CH)为封端配体的未取代咪唑(Im)桥联铜(II)配合物：[Cu(μ-im)(Pz3CH)]nXn(X=BF4(1)，ClO4(2)，CF3SO3(3)，(SO4)0.5(4))。它们的晶体结构已经确定，尽管它们有不同的空间群(1-3的Pna21和单斜的P21/nfor4)和不同的反阴离子，但它们都是等间距的聚合链。铜离子In 1-3具有准六配位环境，而In 4具有近五配位环境。用Bonner-Fisher模型计算得到1-4的交换耦合参数分别为2J/kB=−98.2(16)，−106.6(10)，−102.0(6)和−104.2(8)K。强交换耦合起源于尼姆原子的赤道配位。我们发现J值的大小受反阴离子的影响。证明了中性pz3CH封端配体和阴离子pz3BH−的可用性。
Four kinds of non-substituted imidazolate(im)-bridged copper(II) complexes using tris(1-pyrazolyl)methane (pz3CH) as a capping ligand, namely, [Cu(μ-im)(pz3CH)]nXn(X = BF4(1), ClO4(2), CF3SO3(3), (SO4)0.5(4)) were prepared. Their crystal structures have been determined, and despite the different space groups (orthorhombicPna21for1–3and monoclinicP21/nfor4) and the variety of counter anions, they consist of equally-spacing polymeric chains. The Cu ion in1–3has a quasi-six-coordination environment, while the Cu ion in4has a nearly five-coordination one. The Bonner-Fisher model gave the exchange coupling parameters 2J/kB= −98.2(16), −106.6(10), −102.0(6), and −104.2(8) K for1–4, respectively. The strong exchange couplings originate in the equatorial coordination of the Nimatoms. We revealed that the magnitude ofJvalues is influenced by the counter anion. The usability of the neutral pz3CH capping ligand as well as anionic pz3BH−has been shown.