Unprecedented Trapping of Difluorooctamolybdate Anions within an 伪-Polonium Type Coordination Network

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• 作者：Olena V. Sharga ; Andrey B. Lysenko ; Marcel Handke ; Harald Krautscheid ; Eduard B. Rusanov ; Alexander N. Chernega ; Karl W. Kr盲mer ; Shi-Xia Liu ; Silvio Decurtins ; Adam Bridgeman ; Konstantin V. Domasevitch
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：August 5, 2013
• 年：2013
• 卷：52
• 期：15
• 页码：8784-8794
• 全文大小：606K
• 年卷期：v.52,no.15(August 5, 2013)
• ISSN：1520-510X

文摘

New fluorinated hybrid solids [Mo<sub>2sub>F<sub>2sub>O<sub>5sub>(tr<sub>2sub>pr)] (1), [Co<sub>3sub>(tr<sub>2sub>pr)<sub>2sub>(MoO<sub>4sub>)<sub>2sub>F<sub>2sub>]路7H<sub>2sub>O (2), and [Co<sub>3sub>(H<sub>2sub>O)<sub>2sub>(tr<sub>2sub>pr)<sub>3sub>(Mo<sub>8sub>O<sub>26sub>F<sub>2sub>)]路3H<sub>2sub>O (3) (tr<sub>2sub>pr = 1,3-bis(1,2,4-triazol-4-yl)propane) were prepared from the reaction systems consisting of Co(OAc)<sub>2sub>/CoF<sub>2sub> and MoO<sub>3sub>/(NH<sub>4sub>)<sub>6sub>Mo<sub>7sub>O<sub>24sub>, as Co<sup>IIsup> and Mo<sup>VIsup> sources, in water (2) or in aqueous HF (1, 3) employing mild hydrothermal conditions. The tr<sub>2sub>pr ligand serves as a conformationally flexible tetradentate donor. In complex 1, the octahedrally coordinated Mo atoms are linked in the discrete corner-sharing {Mo<sub>2sub>(渭<sub>2sub>-O)F<sub>2sub>O<sub>4sub>N<sub>4sub>} unit in which a pair of tr-heterocycles (tr = 1,2,4-triazole) is arranged in cis-positions opposite to 鈥渕olybdenyl鈥?oxygen atoms. The anti鈥?i>anti conformation type of tr<sub>2sub>pr facilitates the tight zigzag chain packing motif. The crystal structure of the mixed-anion complex salt 2 consists of trinuclear [Co<sub>3sub>(渭<sub>3sub>-MoO<sub>4sub>)<sub>2sub>(渭<sub>2sub>-F)<sub>2sub>] units self-assembling in Co<sup>IIsup>-undulating chains (Co路路路Co 3.0709(15) and 3.3596(7) 脜), which are cross-linked by tr<sub>2sub>pr in layers. In 3, containing condensed oxyfluoromolybdate species, linear centrosymmetric [Co<sub>3sub>(渭<sub>2sub>-tr)<sub>6sub>]<sup>6+sup> SBUs are organized at distances of 10.72鈥?2.45 脜 in an 伪-Po-like network using bitopic tr-linkers. The octahedral {N<sub>6sub>} and {N<sub>3sub>O<sub>3sub>} environments of the central and peripheral cobalt atoms, respectively, are filled by triazole N atoms, water molecules, and coordinating [Mo<sub>8sub>O<sub>26sub>F<sub>2sub>]<sup>6鈥?/sup> anions. Acting as a tetradentate O-donor, each difluorooctamolybdate anion anchors four [Co<sub>3sub>(渭<sub>2sub>-tr)<sub>6sub>]<sup>6+sup> units through their peripheral Co-sites, which consequently leads to a novel type of a two-nodal 4,10-c net with the Schl盲fli symbol {3<sup>2sup>.4<sup>3sup>.5}{3<sup>4sup>.4<sup>20sup>.5<sup>16sup>.6<sup>5sup>}. The 2D and 3D coordination networks of 2 and 3, respectively, are characterized by significant overall antiferromagnetic exchange interactions (J/k) between the Co<sup>IIsup> spin centers on the order of 鈭? and 鈭? K. The [Mo<sub>8sub>O<sub>26sub>F<sub>2sub>]<sup>6鈥?/sup> anion is investigated in detail by quantum chemical calculations.