Is [Co(4)(H(2)O)(2)(α-PW(9)O(34))(2)](10-) a genuine molecular catalyst in photochemical water oxidation? Answers from time-resolved hole scavenging experiments

Water oxidation catalysts: evolution of [Co(4)(H(2)O)(2)(α-PW(9)O(34))(2)](10-) to catalytically active species is assessed by laser flash photolysis in sacrificial photocatalytic cycles with Ru(bpy)(3)(2+) as a photosensitizer.     

THE CRYSTALLIZATION BEHAVIOR OF [cis-α-Co(trien)(OX)lCl 2H2O (I), [cis-α-Co(trien)(NO2)2]BF4 (II), [cis-α-Co(trien)(NO2)2]-(cis-α-Co(trien)(OX)]Cl l/2SiF6 (III)

Abstract

Three new compounds were synthesized and their crystal structures determined. For compound (I). [cis-α-Co(trien)(OX)]Cl 2H₂O, CoClO₆N₄C₈H₂₂, triclinic, space group P-l (No. 2) a = 6.980(5), b = 8.801(4), c = 12.554(8) Å, α = 89.07(5)°, ? = 75.74(4)°, γ = 81.44(5)°, V = 738.9(8) ų, cell dimensions were obtained from 24 reflections giving FW = 364.4, Z = 2, F[000) = 380.06, Dcalc=1.634mg m-³, μ = 1.36mm-¹. A total of 1907 data were collected over the range of 4° ≤ 2θ ≤ 45°; of these, 1647 (independent and I≥3σ(I)) were used in the structure analysis. Data were corrected for absorption; transmission coefficients ranged from 0.51754 to 0.73648. The final RF and Rw residuals were 0.033 and 0.042.

For compound (II), [cis-α-Co(trien)(NO₂)₂]BF₄, CoN₆C₆O₄BF₄H₁₈, orthorhombic space group Pbca (No. 61) α= 12.260(10), b=12.880(14), c= 17.940(14)A F=2833(4)A³, cell dimensions were obtained from 24 reflections with 2θ in the range of 4.00–45.00 degrees, FW = 383.98, Z = 8, F(000) = 1571.52, Dcalc= 1.801 mgirT³, μ=1.28mm^_1, λ = 0.70930 Å. A total of 1637 data were collected over the range of 4° ≤ 2θ ≤ 45°; of these, 883 (independent and I≥ 2.5σ(I)) were used in the structure analysis. The final RF and Rw residuals were 0.122 and 0.132.

For compound (III), [cis-α-Co(trien)(OX)][cis-α-Co(trien)(NO₂)₂]Cl-l/2SiF₆, Co₂ClSi-l/2N₁₀C₁₄F₃O₁₂H₃₆, orthorhombic, space group Pbca (No. 61) a = 12.804(10), b= 16.543(10), c = 27.419(23) A, V= 5808(7) ų, cell dimensions were obtained from 25 reflections, FW = 760.85, Z = 8, F(000) = 3136.06, Dcalc= 1.740mg m^?3, 4mU= 1.34 mm-¹, λ = 0.70930 Å. A total of 2657 data were collected over the range of 4° ≤ 2θ ≤ 40°; of these, 1902 (independent and I≥ 2.5σ(I)) were used in the structure analysis. The final RF and Rw residuals were 0.058 and 0.062.     

Organophosphoryl polyoxotungstates α-[R2PW9O34]5− [R = PhP(S), C6H11P(O), H2NCH(n-Pr)P(O)]

Tetrabutylammonium salts of organophosphoryl derivatives of tungstophosphate of formula α-[R₂PW₉O₃₄]⁵⁻ [R = PhP(S), C₆H₁₁P(O), H₂NCH(n-Pr)P(O)] have been prepared, purified and characterized by elemental analysis, i.r., ³¹P- and ¹⁸³W-n.m.r. spectroscopy. These anions consist of an α-[PW₉O₃₄]⁹⁻ framework on to which are grafted two equivalent organophosphoryl groups through P–O–W bridges; these new species still retain the ‘unsaturated’ Keggin structure. The five-line ¹⁸³W spectra indicates that the hybrid anions possess C _s symmetry in acetonitrile. This revised version was published online in June 2006 with corrections to the Cover Date.     

A new mixed multi-metallic calcium–cobalt-phosphotungstate with nano wheel-like polyanion: Na6Ca3[Ca2(H2O)6Co9(OH)3(H2O)6(HPO4)2(PW9O34)3]

A new 3-D wheel-like calcium–cobalt phosphotungstate, Na₆Ca₃[Ca₂(H₂O)₆Co₉(OH)₃(H₂O)₆(HPO₄)₂(PW₉O₃₄)₃], is reported and characterized by IR, UV, and single-crystal X-ray diffraction. The crystal structure consists of an infinite 3-D array of [Ca₂(H₂O)₆Co₉(OH)₃(H₂O)₆(HPO₄)₂(PW₉O₃₄)₃]^12? anions (1) connected by sodium and calcium metal cations. The novel feature is the presence of two Ca²⁺, bonded to oxygen of HPO^4? and to H₂O spanning opposite sides in the complex anion. The stability of the crystalline product and its morphology were studied by SEM-EDX and DSC techniques.     

hree Inorganic-organic Composite Polyoxotungstates:Syntheses, Characterization and Structures of [Cu(2,2'-bpy)2]5[α-PW11.5Cu0.5O40]·2H2O,[Co(2,2'-bpy)2(N3)2]4H3[α-PW12O40]·3H2O and [Cu(2,2'-bpy)2(4,4'-bpy)]2[α-GeW12O40]·4H2O

Three new inorganic-organic composite polyoxotungstates [Cu(2,2'- bpy)2]5[α- PW11.5Cu0.5O40]·2H2O 1, [Co(2,2'-bp3)2(N3)2]4H3[α-PW12O40]·3H2O 2 and [Cu(2,2'-bpy)2(4,4'- bpy)]2[α-GeW12O40].4H2O 3 (2,2'-bpy = 2,2'-bipyridine, 4,4'-bpy = 4,4'-bipyridine) have been hydrothermally synthesized and structurally characterized. 1 crystallizes in the orthorhombie space group Pna21 with α = 27.847(3), b = 21.597(2), c = 20.1179(19) A, V = 12099(2) A3, Z = 4, GOF= 1.038, R = 0.0427 and wR = 0.1035; 2 belongs to the triclinic space group P1 with a= 12.31150(10), b = 16.1954(4), c = 19.36290(10) A, α = 99.366(11), β=105.168(8),γ = 111.836(8)°, V = 3309.98(9) A3, Z = 1, GOF = 1.024, R = 0.0739 and wR = 0.2216; and 3 crystallizes in the monoclinic space group P21/n with a = 12.858(4), b = 20.943(6), c = 15.598(5) A, β = 102.338(5)°, V = 4103(2) A3, Z = 2, GOF = 1.026, R = 0.0557 and wR = 0.1316. The common structural features of 1～3 are that their molecular structures all consist of a saturated a-Keggin polyoxoanion and several discrete metal-organic moieties. Intriguingly, 2 and 3 are composed of metal-organic coordination moieties with two mixed ligands.     

Ni(bpy)(H2O)(V2O6)和[Ni(bpy)2]2(V6O17)的水热合成与晶体结构

用NiCl2·6H2O,2,2＇-联吡啶（bpy）,NH4VO3,WO3在443K下通过水热反应法得到了两种多钒酸镍配合物Ni（bpy）（H2O）（V2O6）（1）和[Ni（bpy）2]2（V6O17）（2）．单晶X射线衍射结果表明化合物（1）属于正交晶系,空间群为Pcα2（1）,晶胞参数为0=0．91704（18）nm,b=1．0519（2）nm,c=1．4336（3）nm,V=1．3830（5）nm^3,Z=4;化合物（2）属于单斜晶系,空间群为P2（1）／c,晶胞参数为α=1．5467（3）nm,b=1．4740（3）nm,c=1．0457（2）nm,β=91．99（3）°,V=2．3826（8）nm^3,Z=4．化合物（1）由2,2’-联吡啶修饰的二维[Ni（V2O6）（H2O）]∞电中性层构成,而化合物（2）则由2,2＇-联吡啶修饰的、呈正弦波浪状的[Ni：（V6O17）]∞二维电中性层构成．     

Double sandwich polyoxometalate and its Fe(III) substituted derivative, [As2Fe5Mo21O82]17– and [As2Fe6Mo20O80(H2O)2]16–

A double sandwich polyoxometalate and its Fe(III) substituted derivative, [As(2)Fe(5)Mo(21)O(82)](17-) (1) and [As(2)Fe(6)Mo(20)O(80)(H(2)O)(2)](16-) (2), were synthesized and characterized by single-crystal X-ray diffraction, infrared spectroscopy, fluorescent spectroscopy, UV spectra, thermogravimetry-differential scanning calorimetry analyses, electrospray ionization mass spectrometry, and magnetism measurements. The polyoxoanion is composed of a central fragment FeMo(7)O(28) for 1 (Fe(2)Mo(6)O(26)(H(2)O)(2) for 2) and two external AsMo(7)O(27) fragments linked together by two distinct edge-sharing dimeric clusters Fe(2)O(10) to lead to a C(2v) molecular symmetry. The central FeMo(7)O(28) fragment and external AsMo(7)O(27) fragment have a similar structure, and both of them can be viewed as a monocapped hexavacant α-Keggin subunit with a central FeO(4) group or a central AsO(3) group. Both of the polyoxoanions contain a oxo-bridged Fe(III)(5) magnetic core with the angles of Fe-O-Fe in the range of 96.4(4)-125.7(5)°, and magnetism measurements show an overall ferromagnetic interactions among the five-nuclearity cluster Fe(5) with the spin ground state S = 15/2.     

Syntheses,crystal structures,and magnetic properties of the banana-shaped tungstophosphates: [M6(H2O)2(PW9O34)2(PW6O26)]17− (MII=NiII,CoII)

Two new banana-shaped tungstophosphates [M₆(H₂O)₂(PW₉O₃₄)₂(PW₆O₂₆)]^{17 ?} (M^II?=?Ni^II, Co^II) incorporating two types of lacunary polyoxometalate units have been synthesized in aqueous solution and characterized by elemental analyses, IR, and UV spectra, and single-crystal X-ray diffraction. Structural analyses show that Na₆H₁₁[Ni₆(H₂O)₂(PW₉O₃₄)₂(PW₆O₂₆)]?·?32H₂O (1) and Na₇H₁₀[Co₆(H₂O)₂(PW₉O₃₄)₂(PW₆O₂₆)]?· 31H₂O (2) are generated from two tri-M^II substituted B-α-[(MOH₂)M₂PW₉O₃₄] Keggin units connected by a hexavacant [PW₆O₂₆]^11? Keggin fragment, leading to the M^II-containing banana-shaped tungstophosphates. Magnetic properties of 2 show decrease of the molar magnetic susceptibility at higher temperatures results from spin-orbit coupling of Co^II and antiferromagnetic interactions whereas the maximum at the lower temperatures is indicative of the ferromagnetic interactions within the trinuclear Co^II spin cluster in the sandwich belt.     

Synthesis and Spectroscopic Characterization of Organophosphoryl Polyoxotungstates α-A-[RP(O)]2PW9O5-34

Derivatized polyoxometalates(POMs), especially those including organic and organometallic components, have received current attention due to their potential application in catalysis, medicine and material sciences[1].     

SYNTHESIS AND CHARACTERIZATION OF MANGANESE(III) HYDROXYL-CONTAINING SCHIFF-BASE COMPLEXES: [Mn(III)(Hvanpa)2(NCS)] AND [Mn(III)(Hvanpa)2]Cl · H2O (H2vanpa ˭ 1-(3-METHOXYSALICYLALDENEAMINO)-3-HYDROXYPROPANE)

Abstract

The manganese complexes, [Mn(III)(Hvanpa)₂(NCS)] (1) and [Mn(III)(Hvanpa)₂]Cl · H₂O (2), have been prepared and the crystal structure of complex 2 determined using X-ray crystallography. The monomeric complex has a six-coordinate octahedral geometry. The complex crystallizes in the triclinic space group P-1 with a = 11.446(5) Å, b = 12.782(6) Å, c = 9.023(3) Å, α = 93.92(3)°, β = 97.05(3)°, γ = 65.42(2)°, V = 1169.0(9) ų and Z = 2. The Mn-O and Mn-N distances in the equatorial plane are in agreement with those found for other manganese (III) Schiff-base complexes. In the axial direction, the Mn-O distances of 2.256(3) and 2.236(3) Å, respectively, are about 0.4 Å longer than those in the equatorial plane due to Jahn-Teller distortion at the d ⁴ manganese(III) center. In the crystal, each chloride ion is linked through hydrogen bonding with two hydrogen atoms from the coordinated hydroxyl groups at the apical site. The lattice water molecules also interact with the phenolic oxygen atoms through hydrogen bonding.     

Hexaaquachromium(III) trihydrogen isopolyvanadate [Cr(H2O)6]H3[V10O28] · 2H2O: Synthesis and study

Hexaaquachromium(III) trihydrogen isopolyvanadate [Cr(H₂O)₆]H₃[V₁₀O₂₈] · 2H₂O (I) was obtained and examined by mass spectrometry, X-ray powder diffraction, thermogravimetry, and IR and NMR spectroscopy. The crystals are monoclinic, space group $P\bar 1$ a = 7.862(3), b = 8.427(5), c = 5.000(2) Å, β = 96.46(4)°, V = 867.0(3) ų, ρ_calcd = 5.83 g/cm³, Z = 1.     

Fe(II)LSCo(III)LS]2 ⇔ [Fe(III)LSCo(II)HS]2 photoinduced conversion in a cyanide-bridged heterobimetallic molecular square

The self-assembly of [Fe(III){B(pz)(4)}(CN)(3)](-) and [Co(II)(bik)(2)(S)(2)](2+) affords the diamagnetic cyanide-bridged [Fe(II)(LS)Co(III)(LS)](2) molecular square which is converted into the corresponding magnetic [Fe(III)(LS)Co(II)(HS)](2) species under light irradiation at relatively low temperatures.     

[Ba(18-冠-6)(H2O)(OH)][Fe(NCS)4]的分子和晶体结构

本文用凝胶法培养出18-冠-6钡和硫氰酸铁的配合物单晶, 并用X射线衍射分析了其晶体和分子结构.     

Hydrothermal synthesis and crystal structure of a heteropolyoxotungstate formed by sandwich-type heteropolyanion [Gd(PW11O39)2]11− and reduced [Cu(en)2] + cations

A heteropolyoxotungstate, [Cu(en)₂]₂H₈[Gd(PW₁₁O₃₉)₂] ·?(H₂en)_0.5 ·?3H₂O (1), has been hydrothermally synthesized and characterized by IR, XPS, TGA and single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P 1, with a =?12.651(2) ų, b =?20.559(3) ų, c =?21.729(3) ų, α =?71.379(2), β =?82.829(2), γ =?75.532(2)°, V =?5179.5(14) ų, Z =?2, R ₁ =?0.0702 and ωR ₂ =?0.1479. The heteropolyanion is composed of two monovacant [α-PW₁₁O₃₉]^7? Keggin moieties linked via a Gd atom leading to a sandwich-type structure. The Gd center is in a distorted square antiprismatic coordination environment with eight oxygen atoms, four from each of the two [α-PW₁₁O₃₉]^7?moieties.     

Iron salts with the tetracyanidoborate anion: [Fe(III)(H2O)6][B(CN)4]3, coordination polymer [Fe(II)(H2O)2{κ2N[B(CN)4]}2], and [Fe(II)(DMF)6][B(CN)4]2

The reaction of Fe(OH)(3) with tetracyanidoboronic acid, H[B(CN)(4)]·xH(2)O, in water leads to the first examples of tetracyanidoborates with a triply charged metal cation, [Fe(III)(H(2)O)(6)][B(CN)(4)](3) (1). Using elemental iron powder as starting material, [Fe(II)(H(2)O)(2){κ(2)ΝB(CN)(4)]}(2)] (2) is obtained. Anhydrous iron(II) tetracyanidoborate, which is synthesized by heating of 2, is soluble in dry dimethylformamide. After evaporation of the DMF solvent, single crystals of the third title compound, [Fe(II)(DMF)(6)][B(CN)(4)](2) (3), are obtained. Compound 3 is the first metal tetracyanidoborate soluble in nonpolar solvents. The title compounds have been characterized by single-crystal X-ray diffraction (1 rhombohedral, R3c (no. 167), a = 14.9017(7) ?, c = 20.486(1) ?, Z = 6; 2 tetragonal, I42d (no. 122), a = 12.3662(3) ?, c = 9.2066(4) ?, Z = 4; 3 triclinic, P1 (no. 2), a = 8.6255(3) ?, b = 11.0544(4) ?, c = 12.2377(5) ?, Z = 1). The metal ions in all three compounds are octahedrally coordinated. Whereas 1 and 3 are built up from isolated complex ions, 2 comprises a coordination polymer, in which the Fe(II) ion is coordinated by two oxygen atoms of two water molecules in a trans orientation and four nitrogen donor atoms of the [B(CN)(4)](-) groups, which bridge between neighboring iron ions. The iron(III) ion in 3 is in a perfect octahedral environment, which is formed by the O atoms of 6 molecules of water. The single-crystal X-ray structures, vibrational spectra, thermal properties, solubilities, and electrochemical characteristics are reported and compared with those of other known tetracyanidoborates.     

CLUSTER CONVERSION OF [MoW2O2(O2CEt)9]− TO [MoW2O4(O2 CEt)8]4- BY CHROMIUM HEXACARBONYL CRYSTAL STRUCTURES OF Na[MoW2O2(O2CMe)9] · H2O, [MoW2O2(O2CEt)6(H2O)3] ZnCl4 · 2H2O AND Na2Cr2[MoW2O4(O2CEt)8]2

Abstract

Reactions of Mo(CO)₆ with Na₂WO₄ · 2H₂O in refluxing carboxylic anhydride produce the triangular bioxo-capped mixed-metal carboxylate clusters Na[MoW₂O₂(O₂CR)₉] (R = Me, 1; Et, 2), the propionate being hydrolyzed in 2M HCl containing ZnCl₂ to form [MoW₂O₂(O₂CEt)⁶(H₂O)₃]ZnCl₄·2H₂O (3). Cluster 2 is converted to the incomplete cuboidal tetraanion [MoW₂O₄(O₂CEt)₈]^4- upon reacting with Cr(CO)₆ in propionic anhydride at 120°, the latter species being trapped by Cr^3± and Na^± ions in the reaction mixture to afford the octanuclear heterometallic chain-like cluster Na₂Cr₂ [MoW₂O₄(O₂CEt)₈]₂ (4). Clusters 1, 3 and 4 have been characterized by X-ray crystallography with the following crystal data, for 1: monoclinic, space group P2₁/c, a = 16.666(8), b = 11.096(3), c = 16.541(7) Å, β = 94.60(4)°, V = 3048.9 ų, Z = 4, R, Rw = 0.070, 0.079; for 3, monoclinic, space group Cm, a = 10.259(3), b = 15.756(3), c = 10.870(3) Å, β = 96.18(3)°, V = 1746.8 ų, Z = 2, R, Rw = 0.028, 0.034; for 4, triclinic, space group P-1, a = 13.013(5), b = 14.005(4), c = 12.357(4) Å, α = 109.71(2), β = 117.77(3), γ = 90.41(3)°, V = 1838.9 ų, Z = 1, R, Rw = 0.037, 0.042.     

K15[(LnO)3(PW9O34)2]·xH2O型杂多酸钾的合成与性质

PW9O34^9-阴离子可与镧系元素离子反应生成[(LnO)3(PW9O34)2]^15-型杂多阴离子(Ln=LaCe,Pr,Nd,Sm,Eu,Gd)。^31PNMR测定表明,杂多阴离子中的PW9O34^9-具有A型结构;极谱半波电位、还原电子数及红外光谱测试表明,杂多阴离子中的PW9O34^9-是A,a型异构体。杂多阴离子在水溶液中稳定的pH范围是5.3-8.1,其钾盐的热分解温度约480℃。     

An Organic-inorganic Hybrid Sandwich-type Arsenotungstate [H_2dap]_2H_2[Ni(dap)_2][Ni(dap)_2(H_2O)_2]- [Ni_4(H_2O)_2(B-α-As~VW_9O_(34))_2]·8H_2O

A new organic-inorganic hybrid sandwich-type arsenotungstate[H2dap]2H2[Ni(dap)2] [Ni(dap)2(H2O)2][Ni4(H2O)2(B-α-AsVW9O34)2]·8H2O 1 (dap = 1,2-diaminopropane) has been synthesized by the reaction of Na6[AsIII2W21O69(H2O)]·nH2O, NiCl2·6H2O and dap under hydro- thermal conditions and structurally characterized by elemental analysis, IR spectroscopy, thermo- gravimetric analysis and single-crystal X-ray diffraction. 1 crystallizes in the monoclinic space group P21/n with a = 13.5133(19), b = 19.043(3), c = 17.647(2) , β = 102.585(2)°, V = 4432.0(11) 3, T = 296(2) K, Z = 2, μ = 25.350 mm–1, GOOF = 1.058, R = 0.0353 and wR = 0.0838. The molecular unit of 1 consists of two diprotonated [H2dap]2+ cations, two protons, one four-coordinate [Ni(dap)2]2+ cation, one six-coordinate [Ni(dap)2(H2O)2]2+ cation, one classic tetra-NiII substituted sandwich-type [Ni4(H2O)2(B-α-AsVW9O34)2]10– polyoxoanion and eight lattice water molecules. Furthermore, some reported different types of transition-metal substituted sandwich-type poly- oxoanions are summarized and compared.