Synthesis and crystal structure of mixed metal(III) tungstenyl(VI) ortho-pyrophosphates |
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| Institution: | 1. Inorganic Chemistry Laboratory, Oxford University, South Parks Road, Oxford, OX1 3QR, UK;2. Australian Nuclear Science and Technology Organisation, Lucas Heights, NSW2234, Australia;3. School of Chemistry, The University of Sydney, NSW, 2006, Australia;4. EMAT, University of Antwerp, Groenenborgerlaan 171, 2020, Antwerp, Belgium;1. Center for Crystal Research and Development, Key Laboratory of Functional Crystals and Laser Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, PR China;2. University of Chinese Academy of Sciences, Beijing 100049, PR China;3. State Key Laboratory of Crystal Materials and Institute of Crystal Materials, Shandong University, Jinan 250100, PR China |
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| Abstract: | The series of isotypic anhydrous ortho-pyrophosphates MIII(WVIO2)2(P2O7)(PO4) (M: Sc, V, Cr, Fe, Mo, Ru, Rh, In, Ir) was obtained via vapor phase moderated solid state reactions in sealed ampoules. The crystal structure of the phosphates MIII(WVIO2)2(P2O7)(PO4) (M: V, Ru, Rh) was solved from single crystal X-ray data (C2/c, Z = 16). Fairly regular MO6 and distorted WO6 octahedra share vertices with PO4 and P2O7 units to form a 3D network. For the ortho-pyrophosphates with M: V3+, Cr3+, and Fe3+ the oxidation state of M is confirmed by magnetic measurements. 31P-MAS-NMR spectra of the diamagnetic phosphates MIII(WVIO2)2(P2O7)(PO4) (M: Sc, In, Ir) show surprisingly different isotropic chemical shifts for the seven phosphorus sites. VIII(WVIO2)2(P2O7)(PO4) occurs as equilibrium phase in the quasi-binary system (V1–xWx)OPO4 at x = 0.67 and exhibits a small homogeneity range 0.60 ≤ x ≤ 0.67. The scandium compound shows a fully inverted occupancy of the M sites according to the formulation W(Sc1/2W1/2O2)2(P2O7)(PO4). |
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| Keywords: | Ortho-pyrophosphate Solid state reaction Solid state structure |
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