Ligand Influences on the Structures of Molybdenum Oxide Networks
The influence of organonitrogen ligands on the network structure of molybdenum oxides was examined by preparing three new molybdenum oxide phases [MoO3(4,4‘-bpy)0.5] (MOXI-8), [H x MoO3(4,4‘-bpy)0.5] (MOXI-9), and [MoO3(triazole)0.5] (MOXI-32). The structure of [MoO3(4,4‘-bpy)0.5] consists of layers...
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Published in | Inorganic chemistry Vol. 39; no. 19; pp. 4311 - 4317 |
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Main Authors | , , , , , , |
Format | Journal Article |
Language | English |
Published |
United States
American Chemical Society
18.09.2000
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Online Access | Get full text |
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Summary: | The influence of organonitrogen ligands on the network structure of molybdenum oxides was examined by preparing three new molybdenum oxide phases [MoO3(4,4‘-bpy)0.5] (MOXI-8), [H x MoO3(4,4‘-bpy)0.5] (MOXI-9), and [MoO3(triazole)0.5] (MOXI-32). The structure of [MoO3(4,4‘-bpy)0.5] consists of layers of corner-sharing MoO5N octahedra, buttressed by bridging 4,4‘-bipyridyl ligands into a three-dimensional covalently bonded organic−inorganic composite material. Partial reduction of [MoO3(4,4‘-bpy)0.5] yields the mixed-valence material [H x MoO3(4,4‘-bpy)0.5] (x ≈ 0.5). The most apparent structural change upon reduction is found in the Mo−ligand bond lengths of the MoO5N octahedra, which exhibit the usual (2 + 2 + 2) pattern in [MoO3(4,4‘-bpy)0.5] and a more regular (5 + 1) pattern in [H x MoO3(4,4‘-bpy)0.5]. Substitution of triazole for 4,4‘-bipyridine yields [MoO3(triazole)0.5], which retains the layer motif of corner-sharing MoO5N octahedra but with distinct sinusoidal ruffling in contrast to planar layers of [MoO3(4,4‘-bpy)0.5] and [H x MoO3(4,4‘-bpy)0.5]. The folding reflects the ligand constraints imposed by the triazole ligand that bridges adjacent Mo sites within a layer. MOXI-8, C5H4NMoO3: monoclinic P21/c, a = 7.5727(6) Å, b = 7.3675(7) Å, c = 22.433(3) Å, β = 90.396(8)°, Z = 8. MOXI-9, C5H4.5NMoO3: monoclinic I2/m, a = 5.2644(4) Å, b = 5.2642(4) Å, c = 22.730(2) Å, β = 90.035(1)°, Z = 4. MOXI-32, C2H3N3Mo2O6: orthorhombic Pbcm, a = 3.9289(5) Å, b = 13.850(2) Å, c = 13.366(2) Å, Z = 4. |
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Bibliography: | istex:A7738C960853C6614D42FAD35A8E737234C1DEB4 ark:/67375/TPS-DP5CLCJP-0 ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 0020-1669 1520-510X |
DOI: | 10.1021/ic000496l |