有机功能化混合价态多氧-30-钼轮和中性四钼(V)氧簇。
Organically Functionalized Mixed-Valent Polyoxo-30-molybdate Wheel and Neutral Tetramolybdenum(V) Oxo Cluster.
机构信息
Department of Life Sciences and Chemistry, Jacobs University, Campus Ring 1, Bremen 28759, Germany.
Department of Physics and Earth Sciences, Jacobs University, Campus Ring 1, Bremen 28759, Germany.
出版信息
Inorg Chem. 2022 Aug 1;61(30):11524-11528. doi: 10.1021/acs.inorgchem.2c01236. Epub 2022 Jul 6.
The first organofunctionalized mixed-valent polyoxo-30-molybdate wheel, [MoMoO{AsO(CH)}] (), was synthesized in aqueous, mildly acidic conditions, and upon further acidification, the neutral tetramolybdenum(V) oxo cluster [MoO{AsO(CH)}] () was obtained. Single-crystal X-ray diffraction (XRD) revealed that comprises 18 Mo and 12 Mo ions arranged in a cyclic fashion with alternating {Mo} and {Mo} groups, which are capped by 18 dimethylarsinate ligands, resulting in a novel polyoxo-30-molybdate wheel with a central cavity of ∼1.5 nm. On the other hand, has a distorted-cubic structure, with the corners of the cube being occupied by alternating Mo ions and oxo ligands. The compounds were characterized in solution by H and C NMR and UV-vis spectroscopy and in the solid state by X-ray photoelectron spectroscopy and powder XRD. represents a novel type of polyanionic cycle with manyfold possibilities regarding host-guest chemistry.
首例有机官能化的混合价态多钼氧 30 轮烷，[MoMoO{AsO(CH)}]（），在水相、弱酸性条件下合成，进一步酸化后，得到中性四钼(V)氧簇[MoO{AsO(CH)}]（）。单晶 X 射线衍射（XRD）表明，由 18 个 Mo 和 12 个 Mo 离子以循环方式排列，交替出现{Mo}和{Mo}基团，由 18 个二甲胂酸配体封端，形成了具有约 1.5nm 中心空腔的新型多钼氧 30 轮烷。另一方面，[MoO{AsO(CH)}]具有扭曲的立方结构，立方角由交替的 Mo 离子和氧配体占据。这些化合物在溶液中通过氢和碳 NMR 以及紫外-可见光谱进行了表征，在固态通过 X 射线光电子能谱和粉末 XRD 进行了表征。代表了一种新型的多阴离子环，在主客体化学方面具有多种可能性。
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