Structures and magnetism of {Ni-3}, {Ni-9}, {Ni-5} and {Ni-12} mercapto-tetrazole based clusters
Structures and magnetism of {Ni-3}, {Ni-9}, {Ni-5} and {Ni-12} mercapto-tetrazole based clusters
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{Ni-3}、{Ni-9}、{Ni-5}和{Ni-12}巯基四唑团簇的结构和磁性
DOI：
10.1016/j.poly.2017.11.016
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发表时间：
2018
期刊：
影响因子：
2.6
通讯作者：
Bian He-Dong
中科院分区：
文献类型：
--
作者：
Yao Peng-Fei;Su Chao-Hong;Wu Tai-Xue;Li You;Hao Hong-Mei;Huang Fu-Ping;Yu Qing;Bian He-Dong
四种多核巯基四唑基镍簇，[Ni3(hmt)6(H2O)6]·4H2O (1)、[(C2H5)4N]2[Ni9(μ3-CH3O)8(hmt)12] (2)、[Ni5(μ3-OH)2(Hdmt)6(SCN)8] (3) 和 [Ni12(μ6-CO3)(μ3-CH3O)12(CH3CO2)3(et)6(H2O)12]·Br·2H2O (4), (此处，Hhmt=1-(2-羟乙基)-5-巯基四唑， 合成了Hdmt=1-[2-(N,N-二甲基氨基)乙基]-5-巯基四唑，Het=5-(乙硫基)-1H-四唑)，并通过元素分析、红外、粉末X射线衍射和X射线单晶衍射进行了表征。1显示了中心对称的线性三核镍团簇。2揭示了 具有 S3 对称性的哑铃状 {Ni9} 簇，包含两个 [Ni4(CH3O)4] 立方烷，通过六个“单键 N 单键 N 单键”桥与 Ni 原子连接。3 揭示了具有由μ3-OH−离子支持的领结状骨架的 {Ni5} 簇。4 表现出平面对称性 {Ni12} 簇具有近似三叶形，基于由 aμ6-CO32− 桥接的三个 [Ni4(CH3O)4] 立方烷。结果表明，伴随反应条件（阴离子、溶剂、pH、温度和不同比例）调节的微小配体修饰在自组装过程的结构控制中具有关键作用。还讨论了1、2和4在2-300K范围内的磁性。线性{Ni3} (1) 核通过“单键N单键N单键”桥显示出来自结合模式性质的主要反铁磁相互作用。 {Ni9} (2) 和 {Ni12} (4) 簇通过 µ3-CH3O− 和“单键N单键N单键”桥显示出来自结合模式性质的主要铁磁相互作用。
Four polynuclear mercaptotetrazole-based nickel clusters, [Ni3(hmt)6(H2O)6]·4H2O (1), [(C2H5)4N]2[Ni9(μ3-CH3O)8(hmt)12] (2), [Ni5(μ3-OH)2(Hdmt)6(SCN)8] (3), and [Ni12(μ6-CO3)(μ3-CH3O)12(CH3CO2)3(et)6(H2O)12]·Br·2H2O (4), (here, Hhmt = 1-(2-hydroxyethyl)-5-mercapto-tetrazole, Hdmt = 1-[2-(N,N-dimethylamino)ethyl]-5-mercapto-tetrazole, Het = 5-(ethylthio)-1H-tetrazole), have been synthesized and characterized by elemental analysis, IR, powder X-ray diffraction and X-ray single-crystal diffraction.1shows a centrosymmetric linear trinuclear nickel cluster.2reveals of a dumbbell-like {Ni9} cluster with S3 symmetry containing two [Ni4(CH3O)4] cubanes linked with a Ni atom through six “single bondNsingle bondNsingle bond” bridges.3reveals of a {Ni5} cluster with a bowtie-like skeleton supported byμ3-OH−ions.4exhibits a plane- symmetry {Ni12} cluster with an approximate trefoil shape based on three [Ni4(CH3O)4] cubanes bridged by aµ6-CO32−. The results show that the minor ligand modification accompanying the regulating of reaction conditions (anion, solvent, pH, temperature and the different ratios) have a key role in the structural control of the self-assembly process. Magnetic properties of1,2and4in the 2–300 K have also been discussed. The linear {Ni3} (1) core displays dominant anti-ferromagnetic interactions from the nature of the binding modes through “single bondNsingle bondNsingle bond” bridges. The {Ni9} (2) and {Ni12} (4) clusters display dominant ferromagnetic interactions from the nature of the binding modes throughµ3-CH3O−and “single bondNsingle bondNsingle bond” bridges.