Azide and oxo bridged ferromagnetic clusters: Three face-shared tetracubane Ni(II)/Co(II) hexamers and a wheel-shaped SMM-like Co(II) heptamer

Azide and oxo bridged ferromagnetic clusters: Three face-shared tetracubane Ni(II)/Co(II) hexamers and a wheel-shaped SMM-like Co(II) heptamer
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叠氮化物和氧桥铁磁簇:三个共享面的四立方烷 Ni(II)/Co(II) 六聚体和轮状 SMM 型 Co(II) 七聚体

DOI:
10.1016/j.ica.2008.03.020
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发表时间:
2008-10
影响因子:
2.8
通讯作者:
Gao, Song
Gao, Song
中科院分区:
化学3区
文献类型:
--
作者:
Wang, Bing-Wu;Wang, Xiu-Teng;Zhang, Wen;Wang, Zhe-Ming;Gao, Song

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以Hhdeo (Hhdeo=2-羟基-[1,2-二(吡啶-2-基)]乙烷-1- 1)和叠氮化物为配体,同时构建了四个叠氮化物和氧桥接的多核Ni(II)和Co(II)配合物:[Ni6(Hhdeo)2(hdeo)4(N3)6]·(ClO4)2·2DMF·2H2O(1)]、[Co6(Hhdeo)2(hdeo)4(N3)6]·(ClO4)2·2DMF·2H2O(2))、[Ni6(Hhdeo)2(hdeo)4(N3)6]·(ClO4)2·6H2O(3))和[Co7(hdeo)6(N3)6]·(ClO4)2·2H2O(4))。化合物1 ~ 3均在单斜空间群P21/c中结晶,由μ2、μ3-O和μ2-1、1、μ3-1、1,1- n3桥接的面共四烷六核核组成。化合物4在三斜空间群P1¯中结晶,由μ2-O和μ3-1,1,1-N3桥接的轮状七核核心[Co7(hdeo)6(N3)6]2+组成。对于Co(II),反应溶剂在引导具有六核或七核拓扑结构的最终产物中起重要作用。磁性研究表明,这四种化合物的分子内铁磁(F)耦合是由金属三角单元内不同种类的交换相互作用之间的竞争造成的。在1.9K以上,配合物1-3未观察到单分子磁铁行为。然而,化合物4在静态零和低于4K的600Oe场下表现出明显的缓慢弛豫,趋向于单分子磁铁(SMM)行为。
Four azide and oxo bridged polynuclear Ni(II) and Co(II) complexes have been constructed by the simultaneous use of Hhdeo (Hhdeo=2-hydroxy-[1,2-di(pyridin-2-yl)] ethane-1-one) and azide as ligands: [Ni6(Hhdeo)2(hdeo)4(N3)6]·(ClO4)2·2DMF·2H2O (1), [Co6(Hhdeo)2(hdeo)4(N3)6]·(ClO4)2·2DMF·2H2O (2), [Ni6(Hhdeo)2(hdeo)4(N3)6]·(ClO4)2·6H2O (3) and [Co7(hdeo)6(N3)6]·(ClO4)2·2H2O (4). Compounds 1–3 all crystallize in monoclinic space group P21/c, and consist of face-shared tetracubane hexanuclear cores, which are bridged by μ2, μ3-O and μ2-1,1, μ3-1,1,1-N3. Compound 4 crystallizes in triclinic space group P1¯, and is made up of wheel-like heptanuclear cores [Co7(hdeo)6(N3)6]2+bridged by μ2-O and μ3-1,1,1-N3. For Co(II), the reaction solvents are found to play important roles in directing the final products with hexanuclear or heptanuclear topologies. Magnetic studies demonstrate overall intra-molecular ferromagnetic (F) couplings in these four compounds, which result from, according to our theoretical analysis, the competition between different kinds of exchange interactions within the metallic triangle units. No single-molecule magnet behavior was observed above 1.9K in complex 1–3. However, compound 4 shows significant slow relaxation at static zero and 600Oe fields below 4K, towards single molecule magnet (SMM) behavior.
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