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一些配位过渡金属或稀土连结的多钼酸化合物的合成、结构及性能研究

ISSN号：2095-6134
期刊名称：《中国科学院大学学报》
时间：0
分类：O61[理学—无机化学;理学—化学]
作者机构：[1]中国科学院福建物质结构研究所结构化学国家重点实验室,福州350002
相关基金：supported by the 973 program of the M0ST （001CB 108906）, the National Natural Science Foundation of China （20425313, 90206040, 20333070, 20303021 ）, the Natural Science Foundation of Fujian Province and the Chinese Academy of Sciences

关键词：多钼酸盐, 水热合成, 晶体结构, polyoxomolybdate, hydrothermal synthesis, crystal structure

中文摘要：

利用简单的手性有机配体L-酒石酸成功地合成出了一系列类似DNA螺旋构型的左、右旋的一维链状聚合物：{A[Mo2^ⅥO4Ln^Ⅲ（H2O）6（C4H2O6）2]·4H2O}n（Ln=Sm，Eu，Gd，Ho，Yb，Y；C4H2O6：L-或D-酒石酸；A=NH4或H3O）．通过水热法，巧妙地把传统的钼氧单核{MoO4}、双核{Mo2O7}以及{Mo8O26}等结构单元，通过有机配体配位的过渡金属单元交错地连接成零、一、二、三维的一系列结构新颖的化合物，这类化合物大多数具有可以容纳客体小分子的隧道或空穴，如[Cu（4，4＇-bpy）]：MoO4·2H2O，[Cu（4，4＇-bpy）]：Mo2O8[Cu（4，4＇-bpy）（Hnic）（H2O）]2Mo8O26等．首次利用水热法合成出了含稀土的杂多酸类化合物，[Gd（H2O）3]3[GdMo12O42]·3H2O．该化合物是由Silverton型的[GdMo12O42]^9-阴离子和配位的Gd^3＋阳离子组成的．在[GdMo12O42]^9-离子中首次把顺磁性的钆（Ⅲ）离子引入到该构型的中心，并且通过九配位的钆（Ⅲ）离子把它们连接成具有介孔结构的三维网状化合物．该化合物的获得为今后合成类似化合物提供了一个很好的范例．在水热法合成出的化合物[Cu2（C8H6N2）2（C7H6N2）]2[Mo8O26]中，首次捕捉到喹喔啉的氧化产物苯并咪唑，证明了在水热条件下含氮的芳香杂环类的有机配体可以被二价铜氧化，其氧化产物进而作为配体直接与铜原子配位，最终形成新颖的上述化合物．

英文摘要：

A series of novel double helicates, { A[ Mo^ⅥO4Ln^Ⅲ（H2O）6 （C4H2O6）2 ]·4H2O}n （Ln = Sm, Eu, Gd, Ho, Yb, Y; C4H2O6 = L-tartaric acid; A = NH4 or H3O）, have been synthesized from the reactions of chiral ligands L-tartaric acid with molybdates as well as lanthanide cations. The architectures of these compounds are one dimensional enantiopure novel right- or left-handed double helical one-dimensional chains, which are somehow like DNA in general configurations. By the hydrothermal reaction method, some molybdenum oxide units such as { MoO4}, { Mo2O7}, { Mo8O26} are linked up by transition metal/organic ligand fragments to novel zero-, one-, two- or three-dimensional structures. Most of these compounds have voids, which are occupied by some suitable crystallization molecules. These compounds are： [ Cu（4,4＇-bpy） ]2 MoO4·2H2 O, [ Cu（4,4＇-bpy） ]2 Mo2 07 and [ Cu（4, 4＇-bpy）（Unic）（U2O） ]2Mo8O26. Compound [Gd（H2O）3 ]3 [GdMo12O42 ]·3H2O is the first product in the herterometallate chemistry containing lanthanide cations that is synthesized by the hydrothermal reaction. The compound is built up by Silverton-type [ GdMo12O42 ]^9- anions linking up nine coordinated Gd^3＋ cations. It is the first example for introducing a paramagnetic lanthanide cation into the Silverton-type anionic center, which provides a very interesting example for the further synthesis of such a kind of compound/polymer. One-dimensional polymer, [ Cu2 （C8 H6 N2 ）2 （ C7 H6 N2 ） ]2 [ Mo8O26 ], which consists of β-[ Mo8O26]^4- anions linked by quinoxaline and its oxidized product benzimidazole ligands coordinatingbinuclear copper（Ⅰ） fragments, provides the first example that the isolated copper（Ⅰ） complex under hydrothermal conditions ＂captures＂ the reduction product of original starting organonitrogen ligand to form a copper（Ⅰ）-β-octamolybdate complex.

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