Zhang Han-hui, Lin Zheng-zhong, Huang Chang-cang, Sun Rui-qing, Wu Xiao-yuan, Lin Zhi-hua
Department of Chemistry, Fuzhou University, Fuzhou 350002, China.
Guang Pu Xue Yu Guang Pu Fen Xi. 2004 May;24(5):557-60.
Five novel organic-molybdenum phosphates with [(PO4)4Mo6(V)O15]12- cluster, Na x (H4TETA)3 x (H3O)5 x {Zn[(HPO4)2(PO4)2Mo6O15]2} (2), (H2en)7 x (H3O)4 x {Cu[(HPO4)2(PO4)2Mo6O15]2} x H2O (3), (H3DETA)2 x (H3O)3 x {Co0.5[(HPO4)2(PO4)2Mo6O15]} x H2O (4), [Co(H3TETA)]2{Co0.5[(HPO4)(PO4)3Mo6O15] x 3.5H2O (5) and (H3DETA) x (H3O)4 x {Co1.5 [(HPO4)2(PO4)2Mo6O15]} x 0.5H2O (6), have been synthesized. The relationship between their properties and structures was studied by using FTIR, NIR FT-Raman, UV-Vis DRS and fluorescence etc. In these compounds, every two [(PO4)4Mo6O15] clusters are coordinated by a metal atom to form a {M[(PO4)4Mo6O15]2} dimer. In compound 2, 3 and 4, {M[(PO4)4Mo6O15]2} dimers are hydrogen-bonded by the organic molecules and water molecules to form a three-dimensional expended framework, respectively. In compound 5 and 6, {Co[(PO4)4Mo6O15]2} dimers are coordinated by [Co(H3TETA)] groups and [CoO4] tetrahedra to form a network, respectively. These characteristic vibrational frequencies of the molybdenum phosphates are related to the structure of these compounds. Three characteristic bands in UV-Vis DRS spectra of these compounds have to be attributed to the absorptions of O(d) --> Mo, O(mu) --> Mo and O --> M charge transfer, respectively. These compounds exhibit strong fluorescence emission bands at about 410 nm when excited by 240 nm, which are caused by O(mu) --> Mo charge transfer.
已合成了五种含[(PO4)4Mo6(V)O15]12-簇的新型有机钼磷酸盐，分别为Na x (H4TETA)3 x (H3O)5 x {Zn[(HPO4)2(PO4)2Mo6O15]2} (2)、(H2en)7 x (H3O)4 x {Cu[(HPO4)2(PO4)2Mo6O15]2} x H2O (3)、(H3DETA)2 x (H3O)3 x {Co0.5[(HPO4)2(PO4)2Mo6O15]} x H2O (4)、[Co(H3TETA)]2{Co0.5[(HPO4)(PO4)3Mo6O15] x 3.5H2O (5) 和 (H3DETA) x (H3O)4 x {Co1.5 [(HPO4)2(PO4)2Mo6O15]} x 0.5H2O (6)。通过傅里叶变换红外光谱（FTIR）、近红外傅里叶变换拉曼光谱（NIR FT-Raman）、紫外可见漫反射光谱（UV-Vis DRS）和荧光光谱等方法研究了它们的性质与结构之间的关系。在这些化合物中，每两个[(PO4)4Mo6O15]簇由一个金属原子配位形成{M[(PO4)4Mo6O15]2}二聚体。在化合物2、3和4中，{M[(PO4)4Mo6O15]2}二聚体分别通过有机分子和水分子形成氢键，从而形成三维扩展骨架。在化合物5和6中，{Co[(PO4)4Mo6O15]2}二聚体分别由[Co(H3TETA)]基团和[CoO4]四面体配位形成网络。这些钼磷酸盐的特征振动频率与这些化合物的结构有关。这些化合物的紫外可见漫反射光谱中的三个特征带分别归因于O(d)→Mo、O(μ)→Mo和O→M电荷转移的吸收。当用240 nm激发时，这些化合物在约410 nm处表现出强荧光发射带，这是由O(μ)→Mo电荷转移引起的。
