Synthesis and Structural Characterization of Manganese Carbonyl Incorporated Polyoxomolybdate （n-Bu4N）2 [Mo6O16（OCH3）2 {HOCH2C（CH2O）3}2 {Mn（CO）3}2]

The polyoxoanion incorporated {Mn（CO）3^＋} complex, （n-Bu4N）2[Mo6O16（OCH3）2{HOCH2C（CH2O）3}2·{Mn（CO）3}2]（1）, has been synthesized by the reaction of （n-Bu4N）4[Mo8O26] with Mn（CO）5Br in methanol, in the presence of C（CH2OH）4. The complex 1 has been characterized by IR, UV-Vis, X-ray single crystal diffraction, and TG. Crystal data for the complex 1：C25H48MnMo3NO16 （1）, Triclinic Pi, a=0.9405（3） nm, b=1.3351（4） nm, c=1.5455（4） nm, α=103.206（5）°, β=102.165（5）°, γ=100.784（5）°, V=1.7896（9） nm^3, Z=2, R1=0.0703, wR2= 0.1495. The structure analysis of complex 1 shows that the complex consists of two tetrabutylammonium cations and a polyoxomolybdate anion that incorporates two fac-Mn（CO）3^＋ units. The anion of complex 1 can be considered as the dimer of two rhomb-like anions by sharing of two comers.     

FORMATION OF MOLYBDENUM OXIDE NANOSTRUCTURES CONTROLLED BY POLY(ETHYLENE OXIDE)

Polymeric systems have played an important role as structure-directing agents and in the control of nucleation and growth of crystals.This article reviews the work of our research group in the field of the polymer-assisted crystallization of inorganic materials,mainly focused on the formation of highly ordered,porous molybdenum oxide nanostructures.Different experimental parameters including the influence of poly(ethylene oxide)-containing polymers on the morphology and structure of the products obtained...     

Hybrid Inorganic/Organic Quasi-Single Crystals of Wheel-Shaped \{\hbox{Mo}_{154}\} Macro-anions and Cationic-surfactants

The formation of hybrid inorganic/organic quasi-single crystals from giant polyoxomolybdate (POM) macro-anions in solutions mixed a positively charged surfactant tetradecyltrimethylammonium bromide (TTA⁺Br⁻¹) was described. The crystalline nature of the self-assembled –(TTA)_n complexes was determined by Transmission Electron Microscope (TEM) and Brunauer–Emmett–Teller (BET) analysis. In addition, the quasi-single crystals can further dissolve in aqueous solution with the excess TTABr and the larger hydrophilic aggregations formed. TEM and Dynamic Light Scattering (DLS) investigations were applied to analyze the aggregations in the simple-phase solution.     

Synthesis,structure, and magnetism of four polyoxomolybdate compounds containing yttrium and ytterbium

Four new polyoxometalate compounds consisting of Anderson-type anions and trivalent rare earth (RE) cations, [RE ₂ (H₂O)₁₄M(OH)₆Mo₆O₁₈][M(OH)₆Mo₆O₁₈]?·?14H₂O, RE?=?Y, M?=?Cr(1), Al(2); RE?=?Yb, M?=?Al(3), Cr(4), have been synthesized in aqueous solution and characterized by elemental analyses, infrared (IR) spectra, thermal gravimetric (TG) analyses, and single crystal X-ray diffraction. [M(OH)₆Mo₆O₁₈]^3? as a bidentate ligand coordinates to two RE ^{3 +} , forming a double-supported cation [RE ₂(H₂O)₁₄M(OH)₆Mo₆O₁₈]³⁺. The cations and other [M(OH)₆Mo₆O₁₈]^3? anions in the crystals are linked via hydrogen bonding interactions tightly, forming four supramolecular compounds. The magnetic properties of 1, 3, and 4 have been examined by measuring their magnetic susceptibilities from 2 to 300?K.     

In situ synthesis of an inorganic–organic hybrid based on a molybdenum-oxo chain: [Cu2(pz)(Mo3O10)] n

A polyoxomolybdate, [Cu₂(pz)(Mo₃O₁₀)] _n (pz?=?pyrazine) (1), has been synthesized hydrothermally and characterized by elemental analysis, IR, X-ray photoelectron spectra, and thermogravimetric analysis. Single-crystal X-ray diffraction demonstrates that 1 has a 3-D architecture constructed by combination of {Mo₃O₁₀} units and [Cu₂(pz)]²⁺. All the terminal oxygen atoms of the polyoxomolybdate are coordinated by univalent copper. Pyrazine came from in situ decarboxylation of 2-pyrazinecarboxylic acid and Cu⁺ from the in situ reduction of Cu²⁺ during the hydrothermal synthesis.     

Hydrothermal syntheses, structures and characterizations of three one-dimensional polyoxomolybdates with 4,4′-dimethylenebiphenyl diphosphonic acid as bridge

Three heterometallic 1-D polymers, [{Ni(1,10-phen)₂(H₂O)}₂ {(Mo₅O₁₅)(4,4′-dbp)}·(5.75H₂O)] (4,4′-dbp=O₃PCH₂C₆H₄C₆H₄CH₂PO₃) (1), [{Co(1,10-phen)₂(H₂O)}₂ {(Mo₅O₁₅)(4,4′-dbp)}·(5.5H₂O)] (2) and [{Ni(2,2′-bpy)₃}{Ni(2,2′-bpy)₂(H₂O)} {(Mo₅O₁₅)(4,4′-dbp)}·(4.75H₂O)] (3), have been synthesized under hydrothermal conditions. Their structures were determined by single crystal X-ray diffraction. The 1-D chains is constructed of [Mo₅O₁₅(4,4′-dbp)]⁴⁻ units, which are further decorated and charge compensated by [M(1,10-phen)₂] (M=Ni, Co) or [Ni(2,2′-bpy)₂] subunits. The thermogravimetric analyses and magnetic properties of 1 and 2 were studied.     

The crystal structure of the monohydrate R2Mo6O21·H2O (R=Pr, Nd, Sm, and Eu): a layer structure containing disordered [Mo2O7] groups

Although R₂O₃:MoO₃=1:6 (R=rare earth) compounds are known in the R₂O₃-MoO₃ phase diagrams since a long time, no structural characterization has been achieved because a conventional solid-state reaction yields powder samples. We obtained single crystals of R₂Mo₆O₂₁·H₂O (R=Pr, Nd, Sm, and Eu) by thermal decomposition of [R₂(H₂O)₁₂Mo₈O₂₇]·nH₂O at around 685-715 °C for 2 h, and determined their crystal structures. The simulated XRD patterns of R₂Mo₆O₂₁·H₂O were consistent with those of previously reported R₂O₃:MoO₃=1:6 compounds. All R₂Mo₆O₂₁·H₂O compounds crystallize isostructurally in tetragonal, P4/ncc (No. 130), a=8.9962(5), 8.9689(6), 8.9207(4), and 8.875(2) Å; c=26.521(2), 26.519(2), 26.304(2), and 26.15(1) Å; Z=4; R₁=0.026, 0.024, 0.024, and 0.021, for R=Pr, Nd, Sm, and Eu, respectively. The crystal structure of R₂Mo₆O₂₁·H₂O consists of two [Mo₂O₇]²⁻-containing layers (A and B layers) and two interstitial R(1)³⁺ and R(2)³⁺ cations. Each [Mo₂O₇]²⁻ group is composed of two corner-sharing [MoO₄] tetrahedra. The [Mo₂O₇]²⁻ in the B layer exhibits a disorder to form a pseudo-[Mo₄O₉] group, in which four Mo and four O sites are half occupied. R(1)³⁺ achieves 8-fold coordination by O²⁻ to form a [R(1)O₈] square antiprism, while R(2)³⁺ achieves 9-fold coordination by O²⁻ and H₂O to form a [R(2)(H₂O)O₈] monocapped square antiprism. The disorder of the [Mo₂O₇]²⁻ group in the B layer induces a large displacement of the O atoms in another [Mo₂O₇]²⁻ group (in the A layer) and in the [R(1)O₈] and [R(2)(H₂O)O₈] polyhedra. A remarkable broadening of the photoluminescence spectrum of Eu₂Mo₆O₂₁·H₂O supported the large displacement of O ligands coordinating Eu(1) and Eu(2).     

Synthesis and Structural Characterization of Manganese Carbonyl Incorporated Polyoxomolybdate (n-Bu_4N)_2[Mo_6O_(16)(OCH_3)_2{HOCH_2C(CH_2O)_3}_2{Mn(CO)_3}_2]

The polyoxoanion incorporated {Mn(CO)3+} complex, (n-Bu4N)2[Mo6O16(OCH3)2{HOCH2C(CH2O)3}2· {Mn(CO)3}2](1), has been synthesized by the reaction of (n-Bu4N)4[Mo8O26] with Mn(CO)5Br in methanol, in the presence of C(CH2OH)4. The complex 1 has been characterized by IR, UV-Vis, X-ray single crystal diffraction, and TG. Crystal data for the complex 1: C25H48MnMo3NO16 (1), Triclinic P1, a=0.9405(3) nm, b=1.3351(4) nm, c=1.5455(4) nm, α=103.206(5)o, β=102.165(5)o, γ=100.784(5)o, V=1.7896(9) nm3, Z=2, R1=0.0703, wR...