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

详细信息    查看全文

• 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 [Mo₂F₂O₅(tr₂pr)] (1), [Co₃(tr₂pr)₂(MoO₄)₂F₂]路7H₂O (2), and [Co₃(H₂O)₂(tr₂pr)₃(Mo₈O₂₆F₂)]路3H₂O (3) (tr₂pr = 1,3-bis(1,2,4-triazol-4-yl)propane) were prepared from the reaction systems consisting of Co(OAc)₂/CoF₂ and MoO₃/(NH₄)₆Mo₇O₂₄, as Co^II and Mo^VI sources, in water (2) or in aqueous HF (1, 3) employing mild hydrothermal conditions. The tr₂pr ligand serves as a conformationally flexible tetradentate donor. In complex 1, the octahedrally coordinated Mo atoms are linked in the discrete corner-sharing {Mo₂(渭₂-O)F₂O₄N₄} 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 tr₂pr facilitates the tight zigzag chain packing motif. The crystal structure of the mixed-anion complex salt 2 consists of trinuclear [Co₃(渭₃-MoO₄)₂(渭₂-F)₂] units self-assembling in Co^II-undulating chains (Co路路路Co 3.0709(15) and 3.3596(7) 脜), which are cross-linked by tr₂pr in layers. In 3, containing condensed oxyfluoromolybdate species, linear centrosymmetric [Co₃(渭₂-tr)₆]⁶⁺ SBUs are organized at distances of 10.72鈥?2.45 脜 in an 伪-Po-like network using bitopic tr-linkers. The octahedral {N₆} and {N₃O₃} environments of the central and peripheral cobalt atoms, respectively, are filled by triazole N atoms, water molecules, and coordinating [Mo₈O₂₆F₂]^{6鈥?/sup> anions. Acting as a tetradentate O-donor, each difluorooctamolybdate anion anchors four [Co₃(渭₂-tr)₆]6+ 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 {32.43.5}{34.420.516.65}. The 2D and 3D coordination networks of 2 and 3, respectively, are characterized by significant overall antiferromagnetic exchange interactions (J/k) between the CoII spin centers on the order of 鈭? and 鈭? K. The [Mo₈O₂₆F₂]6鈥?/sup> anion is investigated in detail by quantum chemical calculations.}