Investigations into the Engineering of Inorganic/Organic Solids:  Hydrothermal Synthesis and Structure Characterization of One-Dimensional Molybdenum Oxide Polymers

Abstract

Two one-dimensional intercalating molybdenum oxide polymers have been synthesized using different structure-directing units under specific hydrothermal conditions. MoO-0 (NaNH4Mo3O10) was synthesized using tetramethylammonium hydroxide, and MoO-1(C6H18N2Mo4O13) was synthesized using 1,6-hexanediamine. The two crystal structures have been determined by the single-crystal X-ray diffraction method. Both consist of bundles of parallel molybdenum oxide chains interspersed with metals or organic cations which play the role of intercalating agent in the host structure. The Mo has a 6+ valence state and distorted octahedral coordination. Mo-0 has orthorhombic symmetry (Pnma, No. 62) with a = 8.407(2) Å, b = 7.603(2) Å, and c = 14.350(3) Å. MoO-1 has triclinic symmetry (P1̄, No. 2) with a = 8.267(2) Å, b = 8.986(2) Å, c = 12.714(3) Å, α = 87.58(3)°, β = 76.48(3)°, γ = 67.97(3)°. The study suggests that the structures and properties of intercalation-type molybdenum oxide polymers can be engineered by incorporating the structure-directing units, acidity, and the hydrothermal conditions.

Controllable size, shape and morphology of molybdic acid self-aggregated with rhodamine B to construct functional material

“…by hydrogen-bonding or electrostatic interactions. This has resulted in a series of one-dimensional and two-dimensional intercalation-type molybdenum oxide aggregates [28,29]. However, many of these works were focused on tailoring interactions between the MoO 3 colloidal particles depending on the structures, charge, and the roles of the organic components so that a greater control over the selfaggregation of these particles can be obtained, but seldom involved in the photoelectronic functional properties of organic compositions.…”

A novel 1D molybdenum oxide ribbon bridged by pyridine-4-carboxylic ligands: [(C6H4NO2) Mo2O5OH]

“…Organic components are employed in the formation of oxide skeletons as structure-directing agents [2]. The structural influences of the organic agents are manifest in the compounds of [H 3 N(CH 2 ) 2 [3,4]. Organic components also play a variety of roles in these organic-inorganic hybrid materials as charge-compensating cations [5], ligands bonded to the heterometal sites which may be part of a coordination cation or a mononuclear site associated with the molybdenum oxides [6][7][8][9] and ligands bonded directly to a molybdenum site of the molybdenum oxide skeletal backbone [10,11].…”

“…3). The quadrangle of Mo1AO1AMo1AAO1A between the aforementioned parallelograms is also a parallelogram, and its angles are 73.47(9)°and 106.53 (9) Many molybdenum-oxygen compounds, such as univalent-cation molybdates [4,19], molybdenum oxides/2,2-bipyridinine species [10], possess a variety of infinite 1D chains of linked MoO 6 octahedra and MoO 4 tetrahedra. However, it is noticeable that there are no doubly bridging oxygen atoms in the structure of [(C 6 H 4 NO 2 ) Mo 2 O 5 OH].…”

“…However, it is noticeable that there are no doubly bridging oxygen atoms in the structure of [(C 6 H 4 NO 2 ) Mo 2 O 5 OH]. It seems that the two carboxylic oxygen atoms of a pyridine-4-carboxylic ligand replace a double bridging oxygen atom in the {Mo 4 O 13 } anion chain [4]. Pyridine-4-carboxylic ligands are coordinated to the molybdenum sites and project up and down along the chain alternately.…”

Hydrothermal synthesis and characterization of a novel two-dimensional bimetallic oxide network based on molybdenum oxide chain: [Zn(HPBIM)2(H2O)2Mo6O20]

“…Polymeric structures based on infinite chains of oxomolybdenum polyhedra are often reported as dimolybdate [2], trimolybdate [3][4][5][6], and tetramolybdate systems [7], although pentamolybdate [8] and heptamolybdate [9] systems have been occasionally reported. Examination of crystal structures of these Mo x O nÀ y chains reveals that although these structures share a common onedimensional framework consisting of molybdenum oxide polyhedra, they differ in details of the polyhedral connectivity.…”