Hydrothermal Synthesis and Comparative Coordination Chemistry of New Rare-Earth V4+ Compounds

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• 作者：Martin M. Kimani ; Colin D. McMillen ; Joseph W. Kolis
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：March 19, 2012
• 年：2012
• 卷：51
• 期：6
• 页码：3588-3596
• 全文大小：381K
• 年卷期：v.51,no.6(March 19, 2012)
• ISSN：1520-510X

文摘

Several new hydrated rare earth vanadates and rare earth oxy-vanadates have been synthesized using hydrothermal techniques and characterized using single crystal and powder X-ray diffraction and infrared and UV鈥搗is absorption spectroscopies. The hydrated rare earth vanadates adopt the space group P2₁/m with general formula A₃VO₅(OH)₃ (A = Y (1), Dy (2), or La (3)) and contain anionic distorted square pyramidal [VO₅]^鈭? units and AO₇ and AO₈ polyhedra. The oxy-vanadates with the general formula A₂O(VO₄) (A = Y (4), Dy (5; 6), or Yb (7)) form two polymorphs in either P2₁/c or C2/c space groups and contain anionic tetrahedral [VO₄]^鈭? units and nonvanadium bonded O^{2鈥?/sup> anions in distorted [OA₄] tetrahedra. In all cases, the vanadium ion is in the tetravalent oxidation state, and its original source was the trace V4+ impurities in YVO₄. The observed vanadyl and equatorial vanadium鈥搊xygen bond lengths about the square pyramid in compounds 1鈥?b>3 and the tetrahedral vanadium coordination found in compounds 4鈥?b>7 are unusual for V4+. The electronic and vibrational spectra are also reported and correlated with the appropriate coordination environment.}