Derakhshanrad Shadi, Mirzaei Masoud, Najafi Atefeh, Ritchie Chris, Bauzá Antonio, Frontera Antonio, Mague Joel T
Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, Iran.
School of Chemistry, The University of Melbourne, Victoria 3010, Australia.
Acta Crystallogr C Struct Chem. 2018 Nov 1;74(Pt 11):1300-1309. doi: 10.1107/S2053229618009580. Epub 2018 Oct 17.
As an extension of our continued interest in the preparation of inorganic-organic hybrids, we report the successful hydrothermal synthesis of sodium tris[triaqua(μ-1,10-phenanthroline-2,9-dicarboxylato)dysprosium(III)] silicododecatungstate dodecahydrate, {[DyNa(CHNO)(HO)(SiWO)]·12HO} or Na[Dy(PDA)(HO)][SiWO]·12HO (1), and sodium aqua tris[tetraaqua(μ-4-hydroxypyridine-2,6-dicarboxylato)praseodymium(III)] silicododecatungstate dodecahydrate, {[NaPr(CHNO)(HO)(SiWO)]·12HO} or Na(HO)[Pr(pydc-OH)(HO)][SiWO]·12HO (2) (in which HPDA is 1,10-phenanthroline-2,9-dicarboxylic acid and Hpydc-OH is 4-hydroxypyridine-2,6-dicarboxylic acid or chelidamic acid). Both compounds have been characterized using elemental analysis, IR spectroscopy and X-ray diffraction methods. Structural characterization by single-crystal X-ray diffraction reveals that these compounds consist of [SiWO] Keggin-type polyoxometalates (POMs), where a single {WO} triad is decorated with a trinuclear Ln complex. Moreover, the decorated polyanions are involved in a series of intermolecular interactions, such as hydrogen bonds and anion-π interactions, resulting in three-dimensional supramolecular architectures. Density functional theory (DFT) studies were conducted to support these intermolecular interactions in both 1 and 2, and have been rationalized using molecular electrostatic potential (MEP) surface calculations.
作为我们对无机-有机杂化物制备持续关注的延伸，我们报道了三水合三[三水合(μ-1,10-菲咯啉-2,9-二羧酸根)镝(III)]硅十二钨酸钠十二水合物{[DyNa(C₁₂H₈N₂O₄)(H₂O)₃][SiW₁₂O₄₀]}·12H₂O或Na₃[Dy(PDA)₃(H₂O)₃][SiW₁₂O₄₀]·12H₂O (1)以及水合三水合三[四水合(μ-4-羟基吡啶-2,6-二羧酸根)镨(III)]硅十二钨酸钠十二水合物{[NaPr(C₇H₄NO₅)(H₂O)₄][SiW₁₂O₄₀]}·12H₂O或Na(H₂O)[Pr(pydc-OH)₃(H₂O)₄][SiW₁₂O₄₀]·12H₂O (2)（其中HPDA为1,10-菲咯啉-2,9-二羧酸，Hpydc-OH为4-羟基吡啶-2,6-二羧酸或螯合胺酸）的成功水热合成。这两种化合物均已通过元素分析、红外光谱和X射线衍射方法进行了表征。单晶X射线衍射的结构表征表明，这些化合物由[SiW₁₂O₄₀] 型Keggin结构多金属氧酸盐（POMs）组成，其中单个{WO₆}三元组被一个三核Ln配合物修饰。此外，修饰后的多阴离子参与了一系列分子间相互作用，如氢键和阴离子-π相互作用，从而形成了三维超分子结构。进行了密度泛函理论（DFT）研究以支持1和2中的这些分子间相互作用，并已使用分子静电势（MEP）表面计算进行了合理化解释。
