WestCHEM, School of Chemistry, The University of Glasgow, Scotland, UK.
Chemistry. 2012 Oct 22;18(43):13743-54. doi: 10.1002/chem.201200912. Epub 2012 Sep 20.
Five mixed-metal mixed-valence Mo/V polyoxoanions, templated by the pyramidal SeO(3)(2-) heteroanion have been isolated: K(10)[Mo(VI)(12)V(V)(10)O(58)(SeO(3))(8)]⋅18 H(2)O (1), K(7)[Mo(VI)(11)V(V)(5)V(IV)(2)O(52)(SeO(3))]⋅31 H(2)O (2), (NH(4))(7)K(3)[Mo(VI)(11)V(V)(5)V(IV)(2)O(52)(SeO(3))(Mo(V)(6)V(V)-O(22))]⋅40 H(2)O (3), (NH(4))(19)K(3)[Mo(VI)(20)V(V)(12)V(IV)(4)O(99)(SeO(3))(10)]⋅36 H(2)O (4) and [Na(3)(H(2)O)(5){Mo(18-x)V(x)O(52)(SeO(3))} {Mo(9-y)V(y)O(24)(SeO(3))(4)}] (5). All five compounds were characterised by single-crystal X-ray structure analysis, TGA, UV/Vis and FT-IR spectroscopy, redox titrations, and elemental and flame atomic absorption spectroscopy (FAAS) analysis. X-ray studies revealed two novel coordination modes for the selenite anion in compounds 1 and 4 showing η,μ and μ,μ coordination motifs. Compounds 1 and 2 were characterised in solution by using high-resolution ESI-MS. The ESI-MS spectra of these compounds revealed characteristic patterns showing distribution envelopes corresponding to 2- and 3- anionic charge states. Also, the isolation of these compounds shows that it may be possible to direct the self-assembly process of the mixed-metal systems by controlling the interplay between the cation "shrink-wrapping" effect, the non-conventional geometry of the selenite anion and fine adjustment of the experimental variables. Also a detailed IR spectroscopic analysis unveiled a simple way to identify the type of coordination mode of the selenite anions present in POM-based architectures.
五种由金字塔形 SeO(3)(2-)杂阴离子模板的混合金属混合价态 Mo/V 多氧阴离子，已经被分离出来：K(10)[Mo(VI)(12)V(V)(10)O(58)(SeO(3))(8)]⋅18 H(2)O (1)、K(7)[Mo(VI)(11)V(V)(5)V(IV)(2)O(52)(SeO(3))]⋅31 H(2)O (2)、(NH(4))(7)K(3)[Mo(VI)(11)V(V)(5)V(IV)(2)O(52)(SeO(3))(Mo(V)(6)V(V)-O(22))]⋅40 H(2)O (3)、(NH(4))(19)K(3)[Mo(VI)(20)V(V)(12)V(IV)(4)O(99)(SeO(3))(10)]⋅36 H(2)O (4) 和 [Na(3)(H(2)O)(5){Mo(18-x)V(x)O(52)(SeO(3))} {Mo(9-y)V(y)O(24)(SeO(3))(4)}] (5)。所有这五个化合物都通过单晶 X 射线结构分析、TGA、UV/Vis 和 FT-IR 光谱、氧化还原滴定以及元素和火焰原子吸收光谱（FAAS）分析进行了表征。X 射线研究表明，在化合物 1 和 4 中，硒酸盐阴离子具有两种新的配位模式，表现出 η,μ 和 μ,μ 配位基序。通过使用高分辨率 ESI-MS 对化合物 1 和 2 进行了溶液表征。这些化合物的 ESI-MS 谱显示出与 2-和 3-阴离子电荷状态相对应的分布包络。此外，这些化合物的分离表明，通过控制阳离子“收缩包裹”效应、硒酸盐阴离子的非常规几何形状以及精细调节实验变量之间的相互作用，可能可以指导混合金属体系的自组装过程。此外，详细的红外光谱分析揭示了一种简单的方法，可以识别 POM 基架构中硒酸盐阴离子的配位模式类型。
