Structural refinement of T{sub 2}Mo{sub 3}O{sub 8} (T=Mg, Co, Zn and Mn) and anomalous valence of trinuclear molybdenum clusters in Mn{sub 2}Mo{sub 3}O{sub 8}

Journal Article · Mon Feb 15 00:00:00 EST 2010 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2009.11.024· OSTI ID:21372494

Abe, Hideki ^[1]; Sato, Akira; Tsujii, Naohito; Furubayashi, Takao; Shimoda, Masahiko ^[1]

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1. National Institute for Materials Science (NIMS), Sengen 1-2-1, Tsukuba, Ibaraki 305-0047 (Japan)

Crystal structure of a series of mixed-metal oxides, T{sub 2}Mo{sub 3}O{sub 8} (T=Mg, Co, Zn and Mn; P6{sub 3}mc; a=5.7628(1) A, c=9.8770(3) A for Mg{sub 2}Mo{sub 3}O{sub 8}; a=5.7693(3) A, c=9.9070(7) A for Co{sub 2}Mo{sub 3}O{sub 8}; a=5.7835(2) A, c=9.8996(5) A for Zn{sub 2}Mo{sub 3}O{sub 8}; a=5.8003(2) A, c=10.2425(5) A for Mn{sub 2}Mo{sub 3}O{sub 8}) was investigated by X-ray diffraction on single crystals. Structural analysis, magnetization measurements, X-ray photoemission spectroscopy and cyclic voltammetry showed that the Mn ions at the tetrahedral and octahedral sites in Mn{sub 2}Mo{sub 3}O{sub 8} adopt different valences of +2 and 2+delta (delta>0), respectively. The formal valence of the Mo{sub 3} in Mn{sub 2}Mo{sub 3}O{sub 8} is 12-delta to retain electric neutrality of the compound. In contrast, the T ions and Mo{sub 3} in T{sub 2}Mo{sub 3}O{sub 8} (T=Mg, Co and Zn) adopt the valences of +2 and +12, respectively. - Grapical Abstract: Trinuclear Mo{sub 3} clusters in Mn{sub 2}Mo{sub 3}O{sub 8} adopt an anomalous valence of 12-{approx_equal} ({approx_equal}>0) unlike the Mo{sub 3}{sup 12+} clusters that are usually recognized for Mo{sub 3}-containing inorganic compounds including T{sub 2}Mo{sub 3}O{sub 8} (T=Mg, Co or Zn).

• OSTI ID: 21372494
• Journal Information: Journal of Solid State Chemistry, Vol. 183, Issue 2; Other Information: DOI: 10.1016/j.jssc.2009.11.024; PII: S0022-4596(09)00553-2; Copyright (c) 2009 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
COBALT COMPOUNDS
HEXAGONAL LATTICES
MAGNESIUM COMPOUNDS
MAGNETIZATION
MANGANESE COMPOUNDS
MANGANESE IONS
MOLYBDENUM COMPOUNDS
MONOCRYSTALS
OXIDES
PHOTOEMISSION
SPECTROSCOPY
VALENCE
VOLTAMETRY
X-RAY DIFFRACTION
ZINC COMPOUNDS
ALKALINE EARTH METAL COMPOUNDS
CHALCOGENIDES
CHARGED PARTICLES
COHERENT SCATTERING
CRYSTAL LATTICES
CRYSTAL STRUCTURE
CRYSTALS
DIFFRACTION
EMISSION
IONS
OXYGEN COMPOUNDS
REFRACTORY METAL COMPOUNDS
SCATTERING
SECONDARY EMISSION
TRANSITION ELEMENT COMPOUNDS