Two novel POM-based inorganic-organic hybrid compounds: synthesis, structures, magnetic properties, photodegradation and selective absorption of organic dyes
Two novel POM-based inorganic-organic hybrid compounds: synthesis, structures, magnetic properties, photodegradation and selective absorption of organic dyes
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两种新型POM基无机有机杂化化合物：有机染料的合成、结构、磁性、光降解和选择性吸收
DOI：
10.1039/c5dt01042j
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发表时间：
2015-01-01
影响因子：
4
通讯作者：
Lu, Can-Zhong
中科院分区：
文献类型：
--
作者：
Dui, Xue-Jing;Yang, Wen-Bin;Lu, Can-Zhong
通过（NH 4）（6）Mo 7 O 24中心点4 H（2）O、Cu（Ac）（2）中心点H 2 O和3-bpo配体的混合物在不同温度下的水热反应，分离出两种含有不同但相关的同聚物单元的新型无机-有机杂化材料，[Cu（3-bpo）（H2O）（Mo 4 O 13）]中心点3 H（2）O（1）和[Cu-2（3-bpo）（2）（Mo 6 O20）]（2）。1中的{Mo 4 O 13}（n）链和2中前所未有的[Mo 6 O20]（4-）同聚六钼酸根阴离子通过八面体Cu 2+离子连接成二维杂化层。有趣的是，在1和2中的3-bpo配体位于这些混合层的两侧，并作为拱形的人行桥连接层中的Cu（II）离子通过吡啶基N-供体，并在同一时间连接这些混合层通过弱Mo中心点N-恶二唑键成3D超分子框架。1的另一个重要点是水簇填充在由同聚四氢呋喃单元包围的一维通道中。研究了化合物1的染料吸附性能、光催化性能和化合物1-2的磁性。结果表明，配合物1不仅对橙子（MO）和亚甲基蓝（MB）具有良好的光催化降解性能，而且在室温下对MB具有较高的吸附容量，并能从MB/MO或MB/RhB的混合体系中选择性地捕获MB分子。在适当的过氧化物存在下，吸附在1上的所有MB分子可以完全释放和光降解。磁化率的温度依赖性表明，配合物2表现出反铁磁有序在约5 K，并观察到自旋翻转转变在约5.8 T在2 K，表明从反铁磁到铁磁相的变磁性的行为。
The hydrothermal reactions of a mixture of (NH4)(6)Mo7O24 center dot 4H(2)O, Cu(Ac)(2)center dot H2O and 3-bpo ligands at different temperatures result in the isolation of two novel inorganic-organic hybrid materials containing different but related isopolymolybdate units, [Cu(3-bpo)(H2O)(Mo4O13)]center dot 3H(2)O (1) and [Cu-2(3-bpo)(2)(Mo6O20)] (2). The {Mo4O13}(n) chains in 1 and unprecedented [Mo6O20](4-) isopolyhexamolybdate anions in 2 are linked by octahedral Cu2+ ions into two-dimensional hybrid layers. Interestingly, 3-bpo ligands in both 1 and 2 are located on either side of these hybrid layers and serve as arched footbridges to link Cu(II) ions in the layer via pyridyl N-donors, and at the same time connect these hybrid layers into 3D supramolecular frameworks via weak Mo center dot center dot center dot N-oxadiazole bonds. Another important point for 1 is that water clusters are filled in the 1D channels surrounded by isopolytetramolybdate units. In addition, dye adsorption and photocatalytic properties of 1 and magnetic properties of 1-2 have been investigated. The results indicated that complex 1 is not only a good heterogeneous photocatalyst in the degradation of methyl orange (MO) and methylene blue (MB), but also has high absorption capacity of MB at room temperature and can selectively capture MB molecules from binary mixtures of MB/MO or MB/RhB. All MB molecules absorbed on 1 can be completely released and photodegraded in the presence of adequate peroxide. The temperature dependence of magnetic susceptibility revealed that complex 2 exhibits anti-ferromagnetic ordering at about 5 K, and a spin-flop transition was observed at about 5.8 T at 2 K, indicating metamagnetic-like behaviour from antiferromagnetic to ferromagnetic phases.