Hydrothermal synthesis, structural chemistry, and magnetic properties of materials of the MII/Triazolate/Anion family, where MII = Mn, Fe, and Ni
Hydrothermal synthesis, structural chemistry, and magnetic properties of materials of the MII/Triazolate/Anion family, where MII = Mn, Fe, and Ni
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DOI：
10.1021/ic700790h
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发表时间：
2007-10-29
影响因子：
4.6
通讯作者：
Zubieta, Jon
中科院分区：
文献类型：
--
作者：
Ouelleffe, Wayne;Prosvirin, Andrey V.;Zubieta, Jon
水热化学已被用于制备一系列三氮杂骨架，[Mn-7(TRZ)(8)(CH3CO2)(4)(OH)(2)]中心点2.5H(2)O(1中心点2.5H(2)O)，[Mn-5(Htrz)(2)(SO4)(4)(OH)(2)](2)，[Fe-5(Htrz)(2)(SO4)(4)(OH)(2)[(3)，[Fe-3(Htrz)(3)(HSO4)(SO4)(2)(OH)]中心点H2O(4中心点H2O)，[Ni-3(TRZ)(3)(OH)(3)(H2O)(4)]中心点5H(2)O(5中心点5H(2)O)，和[Ni-3(TRZ)(5)(OH)]中心点2.5H(2)O(6-2.5H(2)O)。这些材料都表现出三维结构，反映了三唑/三氮唑配体连接多个金属位置的趋势。结构的一个显著特征是存在嵌入的金属团簇作为构建块：1中的七核M-II单元，2和3中的五核M-II中心，以及4和5中的三核M-II团簇。2-5中磁性金属阳离子的五核和三核团簇的存在反映在这些材料的异常磁特性中，所有这些都表现出自旋受挫。化合物5-5H(2)O可逆Clesorbs/Sorbs溶剂。然而，脱水相不吸附甲醇、N-2、O-2或H-2，这可能是由于高极性的空穴体积和连接空穴结构的较大空腔的狭窄通道的结果。
Hydrothermal chemistry has been exploited in the preparation of a series of manganese(II), iron(II), and nickel(II) triazolate frameworks, [Mn-7(trZ)(8)(CH3CO2)(4)(OH)(2)]center dot 2.5H(2)O (1 center dot 2.5H(2)O), [Mn-5(Htrz)(2)(SO4)(4)(OH)(2)] (2), [Fe-5(Htrz)(2)(SO4)(4)(OH)(2)[ (3), [Fe-3(Htrz)(3)(HSO4)(SO4)(2)(OH)]center dot H2O (4 center dot H2O), [Ni-3(trz)(3)(OH)(3)(H2O)(4)]center dot 5H(2)O (5 center dot 5H(2)O), and [Ni-3(trz)(5)(OH)]center dot 2.5H(2)O (6-2.5H(2)O). The materials all exhibit three-dimensional structures, reflecting the tendency of triazole/triazolate ligands to bridge multiple metal sites. A prominent characteristic of the structures is the presence of embedded metal clusters as building blocks: heptanuclear Mn-II units in 1, pentanuclear M-II sites in 2 and 3, and trinuclear M-II clusters in 4 and 5. The presence of the pentanuclear and trinuclear clusters of magnetic metal cations in 2-5 is reflected in the unusual magnetic characteristics of these materials, all of which exhibit spin frustration. The compound 5-5H(2)O reversibly clesorbs/sorbs solvent. However, the dehydrated phase does not adsorb methanol, N-2, O-2, or H-2, presumably as a consequence of the highly polar void volume and the narrow channels connecting the larger cavities of the, void structure.