Large Cation−Anion Materials Based on Trinuclear Ruthenium(III) Salts of Keggin and Wells-Dawson Anions Having Water-Filled Channels

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• 作者：Masooma Ibrahim ; Michael H. Dickman ; Andreas Suchopar ; Ulrich Kortz
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：February 16, 2009
• 年：2009
• 卷：48
• 期：4
• 页码：1649-1654
• 全文大小：295K
• 年卷期：v.48,no.4(February 16, 2009)
• ISSN：1520-510X

文摘

Reaction of the trinuclear ruthenium(III) cation [Ru₃O(OOCCH₃)₆(CH₃OH)₃]⁺ with the Keggin-type [α-GeW₁₁O₃₉]⁸⁻, [α-SiW₁₁O₃₉]⁸⁻, and [α-SiMo₁₂O₄₀]⁴⁻ and the Wells−Dawson-type [α-P₂W₁₈O₆₂]⁶⁻ polyanions in an aqueous, acidic medium resulted in plenary polyoxometalate-based materials K₂Na[Ru₃O(OOCCH₃)₆(H₂O)₃][α-GeW₁₂O₄₀]·10H₂O (1), K₃[Ru₃O(OOCCH₃)₆(H₂O)₃][α-SiW₁₂O₄₀]·18H₂O (2), K₃[Ru₃O(OOCCH₃)₆(H₂O)₃][α-SiMo₁₂O₄₀]·7H₂O (3), and K₂Na[Ru₃O(OOCCH₃)₆(H₂O)₃]₃[α-P₂W₁₈O₆₂]·26H₂O (4), respectively. All four materials, 1−4, crystallize as sodium and/or potassium salts in the monoclinic space group P2₁/n. Compounds 1−4 were characterized by IR, thermogravimetric analysis, and single-crystal/powder X-ray diffraction (XRD). The isolated solid-state frameworks, composed of cocrystallized trinuclear ruthenium cations and polyanions, exhibit nanosized voids filled with crystal waters. These water molecules can be removed reversibly upon heating under a vacuum, and powder XRD measurements demonstrated that the crystallinity of the compound was preserved. Sorption studies on ethanol and methanol were also performed.