A New Nitronyl Nitroxide Radical as Building Blocks for a Rare S=13/2 High Spin Ground State 2p-3d Complex and a 2p-3d-4f Chain
A New Nitronyl Nitroxide Radical as Building Blocks for a Rare S=13/2 High Spin Ground State 2p-3d Complex and a 2p-3d-4f Chain
复制标题
一种新的硝基硝基氧自由基作为稀有 S=13/2 高自旋基态 2p-3d 配合物和 2p-3d-4f 链的构建模块
DOI：
10.1021/acs.cgd.6b01276
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发表时间：
2017
影响因子：
3.8
通讯作者：
Cheng Peng
中科院分区：
文献类型：
--
作者：
Yao Binling;Guo Zhilin;Zhang Xuan;Ma Yue;Yang Zhenhao;Wang Qinglun;Li Licun;Cheng Peng
设计并合成了一个新的含氮氧自由基L（L = 2-（4-（5-甲基羰基-3-吡啶基）苯并氧）-4，4，5，5-四甲基咪唑啉-1-氧基-3-氧化物）作为多齿配体，以3d或3d-4f为前体，合成了具有结构和磁性的化合物. Cu（hfac）_2和Gd（hfac）_3·2H_2O（hfac =六氟乙酰丙酮）与L反应，生成了S = 13/2的高自旋基态Cu Ⅱ配合物[（Cu（hfac）_2）_7（L）_6]（1）和Cu Ⅱ-Gd Ⅲ链状配合物[Gd（hfac）_3Cu（hfac）_2（L）_2]_n·0.5CH_2Cl_2（2）。单晶X射线衍射研究表明，配合物1中L自由基的N-O基团均与Cu Ⅱ离子轴向结合，导致Cu Ⅱ与L自由基发生铁磁交换，形成S = 13/2的高自旋基态.在Cu（hfac）2和L自由基体系中加入Gd（hfac）3单元后，得到一维链状结构，并且在链状结构中存在Gd Ⅲ-自由基相互作用和反铁磁自由基-自由基耦合.
A new nitronyl nitroxide radical L (L = 2-(4-(5-methyl-carbonyl-3-pyriyl)benzoxo)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) containing N–O groups and the pyridyl nitrogen group was designed and synthesized as a multidentate ligand to obtain compounds with interesting structures and magnetic properties from 3d or 3d-4f precursors. The reaction of Cu(hfac)2and/or Gd(hfac)3·2H2O (hfac = hexafluoroacetylacetonate) with L resulted in a rareS= 13/2 high spin ground state CuIIcomplex [(Cu(hfac)2)7(L)6] (1) and a CuII–GdIIIchain complex [Gd(hfac)3Cu(hfac)2(L)2]n·0.5CH2Cl2(2). Single crystal X-ray diffraction studies indicate that the N–O groups of the L radicals are all axially bound to CuIIions in complex1, which result in the ferromagnetic exchange between CuIIand radicals and anS= 13/2 high spin ground state. While adding Gd(hfac)3units to the system of Cu(hfac)2and L radical, a one dimension chain structure is obtained, and there are ferromagnetic GdIII-radical interactions and antiferromagnetic radical–radical coupling in the chain.