A study of complexation of chloral hydrate with heteropoly anions having various structures

¹H NMR was applied to study the interaction of chloral hydrate in deuterionitrobenzene solution with tetrabutylammonium salts of the heteropoly acids (HPA) belonging to five structural types: Keggin (H₃PW₁₂O₄₀, H₃PMo₁₂O₄₀, H₄SiW₁₂O₄₀), Dawson (-H₆P₂W₁₈O₆₂, -H₆P₂Mo₁₈O₆₂, -H₄S₂Mo₁₈O₆₂), H₆P₂W₂₁O₇₁(H₂O)₃, H₆As₂W₂₁O₆₉(H₂O), and H₂₁B₃W₃₉O₁₃₂. The surface of the HPA anions is nonuniform in acid-base properties. A general rule for all HPA was found, namely, that the HPA acidity increases with a decrease in the specific anion charge (per W or Mo atom).     

2,5-双(乙炔基二茂铁)噻吩/钨磷杂多酸纳米杂化LB膜的制备与光电性质研究

以含有共轭大π键的2,5-双(乙炔基二茂铁)噻吩(BFET)和二甲基双十八烷基铵(DMDOA)与Keggin结构和Dawson结构钨磷杂多酸做成膜材料, 用LB技术组装了两种新型无机-有机杂化LB膜. 用π-A曲线、UV-vis吸收光谱、原子力显微镜(AFM)、扫描隧道显微镜(STM)、荧光光谱和表面光电压谱(SPS)对标题LB膜的成膜性能、结构及光电性质进行了研究, 发现标题杂化LB膜的粒子具有纳米尺寸, 在可见光区有较强的光电压响应, 在电压为±2.0 V时, 隧道电流值达到±100 nA.     

Synthesis and characterization of one- to three-dimensional compounds composed of paradodecatungstate-B cluster and transition metals as linkers

Three new extended frameworks built from paratungstate and transition metals have been synthesized and characterized. In the compound Na₈[{Cd (H₂O)₂}(H₂W₁₂O₄₂)]·32H₂O (1), two neighboring paratungstate-B ions [H₂W₁₂O₄₂]¹⁰⁻ are linked by [Cd(H₂O)₂]²⁺ units, leading to the formation of infinite one-dimensional (1D) anion chain [{Cd(H₂O)₂}(H₂W₁₂O₄₂)]_n⁸ⁿ⁻. The anion [{Co(H₂O)₃}{Co(H₂O)₄}(H₂W₁₂O₄₂)]_n⁶ⁿ⁻ of the compound Na₆[{Co(H₂O)₃}{Co(H₂O)₄}(H₂W₁₂O₄₂)]·29H₂O (2) shows a layer-like (2D) structure in which paratungstate-B units are linked by CoO₆ octahedra, while the anion [{Co(H₂O)₃}₃(H₂W₁₂O₄₂)]_n⁴ⁿ⁻ of the compound (H₃O⁺)₃[{Na(H₂O)₄}{Co(H₂O)₄}₃(H₂W₁₂O₄₂)]·24.5H₂O (3) is a three-dimensional (3D) anionic polymer that consists of paratungstate-B units linked by CoO₆ octahedra. Compound 3 can reversibly adsorb and desorb water molecules leading to the color reversibly change from pink to violet. The preliminary magnetic measurement and electrochemical properties of compounds are performed. The crystal structure of unexpected product Na₄[NiW₆O₂₄H₆]·13H₂O (4) is described here for the rare report of crystal structure information on the Anderson-type polyoxotungstate which has nickel as a heteroatom.     

Dawson型磷钨杂多阴离子P2W18O626-的电化学性质和对O2还原的电催化作用

用循环伏安、交流伏安和交流阻抗法对Dawson型磷钨杂多阴离子P₂W₁₈O₆₂^6-的电化学性质进行了详细研究, 循环伏安结果显示, P₂W₁₈O₆₂^6-在pH 2.52的0.1 mol·L^-1 Na₂SO₄+NaHSO₄溶液中有两对可逆的单电子还原-氧化波和两对可逆的双电子还原-氧化波. 单电子波的峰电位和电流与溶液的pH无关, 双电子波的峰电位则随溶液pH的增加而负移, 峰电流降低, 表明双电子电极过程有H⁺参与, 其数目为2. 交流阻抗谱表明P₂W₁₈O₆₂^6-的电极过程完全受扩散控制, 实验测定其扩散系数(D_O)为2.5×10^-6 cm²·s^-1. 循环伏安结果表明P₂W₁₈O₆₂^6-的第III对波对O₂还原为H₂O₂具有显著的电催化作用, 催化效率约达300%. 将P₂W₁₈O₆₂^6-应用于PW₁₁O₃₉Fe(III)(H₂O)^4-构成的类电-芬顿过程, 使该过程对硝基苯的降解效率显著提高.     

Dehydrogenation activity and structure of polyaniline supported heteropolyacid catalysts

Polyaniline(PAN) supported H₆P₂W₁₈O₆₂(PW) , H₃PMo₁₂O₄₀ (PMo) and H₄PMo₁₁VO₄₀(PMoV) catalysts were prepared and their activities for hexanol conversion were tested. IR, XRD, ICP and SEM measurements proved that the heteropolyacids (HPA) could be supported on this type of polymer. The PAN supported HPA catalysts exhibit higher redox activities and low acid-base activities for the hexanol conversion. The redox activities increase with increasing amount of the heteropolyacid. Substitution of Mo ion by V ion results in an increase of redox activities of the catalysts. This revised version was published online in June 2006 with corrections to the Cover Date.     

H_6P_2W_(18)O_(62)/SiO_2:用模板剂制备及光催化降解二甲酚橙的性能

分别采用非离子表面活性剂(C_3H_6OC_2H_4O)_x(P123),阴离子表面活性剂C_(12)H_(25)NaO_4S(SDS)和C_(18)H_(29)NaO_3S(SDBS)作为模板剂,通过溶胶-凝胶再结合程序升温溶剂热一步法制备了一系列固载杂多酸光催化材料-H_6P_2W_(18)O_(62)/SiO_2。通过傅立叶-红外光谱(FTIR)、X-射线衍射(XRD)、电感耦合等离子体原子发射光谱(ICP-AES)、氮气吸附-脱附测定、透射电子显微镜(TEM)以及扫描电子显微镜配合X-射线能量色散谱仪(SEM-EDS)等测试手段对不同模板剂作用下合成产物进行了对比表征分析。结果表明,不同模板剂作用下的系列固载杂多酸-H_6P_2W_(18)O_(62)/SiO_2产物中母体多酸的Dawson基本结构均未发生明显变化,但固载后比表面积显著不同,其中,经模板剂P123和SDS作用合成的H_6P_2W_(18)O_(62)/SiO_2(P123)和H_6P_2W_(18)O_(62)/SiO_2(SDS)的比表面积高达916和634m~2·g~(-1),且显示为有序介孔材料。以二甲酚橙为模型分子,在微波场作用下,该系列固载多酸光催化性能研究结果显示,它们的光催化活性可被微波显著增强,其中,采用P123作用合成产物的光催化活性最高,60 min内对二甲酚橙的降解率达99%以上。     

Synthesis and characterization of hybrid materials based on 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and Dawson-type tungstophosphate K7[H4PW18O62]·18H2O and K6[P2W18O62]·13H2O

In this study, we synthesized hybrid materials using well-Dawson polyoxometalates (POMs), K₇[H₄PW₁₈O₆₂]·18H₂O or K₆[P₂W₁₈O₆₂]·13H₂O and a room temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF₄]). K, W, P and CHN elemental analysis showed that one mole of [H₄PW₁₈O₆₂]⁷⁻ reacts with 6 moles of BMIM⁺ and one mole of [P₂W₁₈O₆₂]⁶⁻ reacts with 4 moles of BMIM⁺ to form, respectively, K[BMIM]₆H₄PW₁₈O₆₂ and K₂[BMIM]₄P₂W₁₈O₆₂. X-ray diffraction illustrated amorphous structure of the hybrid materials. FT-IR spectra showed the presence of both 1-butyl-3-methylimidazolium cation and the Dawson anion. TG analysis displayed a relative thermal stability of the hybrid materials compared to the parents Dawson POMs. Cyclic voltammetry showed that the reduction peak potentials of the Dawson anion in the hybrid materials shift towards negative values and the shift is more pronounced for K[BMIM]₆H₄PW₁₈O₆₂ compared to K₂[BMIM]₄P₂W₁₈O₆₂. This was attributed to a decrease in the acidity of the Dawson POM anion in the hybrid material.     

Esterification of n-Butanol with Acetic Acid in the Presence of Heteropoly Acids with Different Structures and Compositions

The esterification reaction of n-butanol with acetic acid ([BuOH] : [HOAc] = 1 : 15 mol/mol; 55°C, 5% H₂O) was studied in the presence of tungsten heteropoly acids of the Keggin (H₃PW₁₂O₄₀, H₄SiW₁₂O₄₀, H₅PW₁₁TiO₄₀, H₅PW₁₁ZrO₄₀, and H₃PW₁₁ThO₃₉) and Dawson structure (-H₆P₂W₁₈O₆₂, H₆P₂W₂₁O₇₁(H₂O)₃, H₆As₂W₂₁O₆₉(H₂O), and H₂₁B₃W₃₉O₁₃₂). The reaction orders with respect to H₆P₂W₂₁O₇₁(H₂O)₃, H₃PW₁₂O₄₀, and H₆P₂W₁₈O₆₉are equal to 0.78, 1.00, and 0.97, respectively. It was found that the reaction rate depends on the acidity, as well as on the structure and composition of heteropoly acids. The H₂₁B₃W₃₉O₁₃₂heteropoly acid is most active, whereas the Keggin-structure heteropoly acids exhibit the lowest activities. Of the Keggin structure heteropoly acids, H₅PW₁₁ZrO₄₀exhibits the highest activity because of the presence of a Lewis acid site in its structure.     

Correlation between reduction potential of vanadium-containing heteropolyacid (HPA) catalysts and their oxidation activity for cyclohexanol dehydrogenation

Vanadium-containing H_6+xP₂Mo_18−xV_xO₆₂ (x = 0, 1, 2 and 3) Wells-Dawson heteropolyacid (HPA) and H_3+xPMo_12−xV_xO₄₀ (x = 0, 1, 2 and 3) Keggin HPA catalysts were applied to the vapor-phase dehydrogenation of cyclohexanol. The catalytic oxidation activity showed a volcano-shaped curve with respect to vanadium substitution for both families of HPA catalysts. The Wells-Dawson HPA showed a better catalytic oxidation performance than the Keggin HPA at the same level of vanadium substitution.     

Keggin类杂多化合物催化环氧化环戊烯的谱学研究

报道了一系列Keggin 类杂多化合物与H₂O₂ (30%)催化氧化环戊烯. 其中两缺位的 [γ-SiW₁₀(H₂O)₂O₃₄](Bu₄N)₄ 的催化活性最好, 环戊烯转化率为90%, 环戊烯环氧化物的选择性为98%. 反应前后的UV-vis, FT-IR分析表明, 反应后催化剂的结构保持, 没有发生降解. 在以磷为中心原子的磷系Keggin 杂多酸复合溴代十六烷基吡啶中, 钼钨混合型的催化活性优于钨磷酸(H₃PW₁₂O₄₀•mH₂O)和钼磷酸(H₃PMo₁₂O₄₀•mH₂O)的. 而在十一种钼钨混合型的含磷杂多化合物H₃PMo_12－nW_nO₄₀•mH₂O中, 当n＝6时的H₃PMo₆W₆O₄₀•mH₂O显示出了最好的活性. 我们采用UV-vis, FT-IR and ³¹P NMR 等谱学方法表征了新鲜的催化剂和处于反应状态下的催化剂. 发现在反应条件H₂O₂ (30%)的量是催化剂的50倍时, H₃PMo₆W₆O₄₀•mH₂O全部降解成数种含磷的物种, 这些含磷物种可能包含反应中最具催化活性的物种. 而在此条件时, 发现H₃PW₁₂O₄₀•mH₂O降解得很少, 只有一种磷钨氧物种生成, 但不是Venturello-Ishii催化体系中的活性物种{PO₄[WO(O₂)₂]₄}^3－.     

The oxidation study of methyl orange dye by hydrogen peroxide using Dawson-type heteropolyanions as catalysts

In this research, the oxidation of an azo dye (methyl-orange) by H₂O₂, in an aqueous solution, using a Dawson-type heteropolyanion (α₂P₂W₁₂Mo₅O₆₁Fe)^7? as catalyst was studied. The effects of different parameters dye oxidation were investigated. The studied parameters were: the initial pH, the initial H₂O₂ concentration, the catalyst mass and the initial dye concentration. The optimal conditions for a maximum discoloration efficiency (100 %) are: pH: 6, [MO]₀ = 2 mg/L, Catalyst (α₂P₂W₁₂Mo₅O₆₁Fe)^7? mass: 1 g, [H₂O₂]₀ =: 0.072 M. The effect of other Dawson-mixed heteropolyanions, such as (αP₂W₁₈O₆₂)^6?, (αP₂W₁₂Mo₆O₆₂)^6? and (α₂P₂W₁₂Mo₅O₆₁X)^n? (X = Ni²⁺,Cr³⁺,Cu²⁺) on the dye oxidation at room temperature was evaluated. The stability of the catalyst after reaction was verified.     

Facile preparation of an α-Keggin-type [H3W12O40] complex: Does it exist in aqueous solution?

The formation processes of α-Keggin-type [H₂W₁₂O₄₀]⁶⁻ and [H₃W₁₂O₄₀]⁵⁻ complexes were investigated in aqueous W^VI (0.05–0.50 M) solutions. The formation of [H₂W₁₂O₄₀]⁶⁻ was ascertained by the appearance of a ¹⁸³W NMR line at −117 ppm, but no evidence was found for the existence of [H₃W₁₂O₄₀]⁵⁻ in the solution at the accessible pH range. The addition of (CH₃)₄N⁺ (Me₄N⁺) to the W^VI solution directly precipitated the (Me₄N)₆[H₂W₁₂O₄₀] salt. On the other hand, the addition of the larger Bu₄N⁺ cation precipitates the (Bu₄N)_4.5H_0.5[H₃W₁₂O₄₀] salt, because a naked proton formed during the crystallization process or in the solid state may enter into the Keggin shell to produce [H₃W₁₂O₄₀]⁵⁻. This explanation is based on the fact that [H₂W₁₂O₄₀]⁶⁻ is not spontaneously converted into [H₃W₁₂O₄₀]⁵⁻ in acidified aqueous solution. On the basis of their voltammetric properties, a simple diagnostic criterion was developed to distinguish between [H₂W₁₂O₄₀]⁶⁻ and [H₃W₁₂O₄₀]⁵⁻.     

Titanium(IV) polynuclear hydroxo complexes stabilized in solution by [PW11O39]7? heteropolyanion

[PW₁₁O₃₉]^7– heteropolyanion (HPA) stabilizes Ti(IV) in aqueous solution at Ti:PW₁₁ ratios from 1 to 12 and pH 1–3. Ti(IV) is completely precipitated under these conditions in the absence of HPA. Differential dissolution phase analysis, optical, IR,³¹P and¹⁷O NMR spectra show that one Ti(IV) ion is incorporated into the Keggin lattice. The other ions, most probably, are located on the HPA surface in the form of oligomeric hydroxo fragments: [PW₁₁Ti^IVO₄₀·Ti_n–1 ^IVO_xH_y]^k–. Both types of Ti(IV) ions bind peroxo groups on interaction of the complex with H₂O₂.     

Two highly connected POM-based hybrids varying from 2D to 3D: The use of the isomeric ligands

Through employing two isomeric ligands, isonicotinic acid (HINA) and nicotinic acid (HNA), with different electron delocalization nature, two high-dimensional hybrids based on highly connected α-metatungstate clusters, [Na₂(H₂O)₈Ag₂(HINA)₃(INA)][Na(H₂O)₂Ag₂(HINA)₄(H₂W₁₂O₄₀)]·2H₂O (1) and [Na₂(H₂O)₄Ag₆(HNA)₂(NA)₂(H₂W₁₂O₄₀)]·8H₂O (2), have been conventionally synthesized and structurally characterized. 1 exhibits an unusual 1D-in-2D pseudo-polyrotaxane entangled structure, namely, the 2D sheets [Na(H₂O)₂Ag₂(HINA)₄(H₂W₁₂O₄₀)]_n³ⁿ⁻ are penetrated by enantiomorphous meso-helical chains [Na₂(H₂O)₈Ag₂(HINA)₃(INA)]_n³ⁿ⁺. In the 2D sheets, each [H₂W₁₂O₄₀]⁶⁻ cluster is surrounded by six Ag and two Na atoms. 2 exhibits a 3D (4, 6)-net structure with (3²6²7²)(3²4⁴5⁴6⁴7)(3²4⁴6⁸7) topology, in which each [H₂W₁₂O₄₀]⁶⁻ cluster is connected with ten Ag atoms. These facts indicate that the isomeric ligands play a key role in the formation of final structures. From 1 to 2, the connection number of the [H₂W₁₂O₄₀]⁶⁻ cluster changes from 8 to 10 and the dimensionality increases from 2 to 3. Moreover, 1 and 2 display photoluminescent properties in the blue range at room temperature.     

Synthesis, crystal structure, and property of one- and two-dimensional complexes based on paradodecatungstate-B cluster

Three polyoxotungstates, Na₈[Cu(H₂O)₂(H₂W₁₂O₄₂)]·30H₂O (1), Na₈[Cd(H₂O)₂(H₂W₁₂O₄₂)]·20H₂O (2), and Na_7.4[Cd_1.3(H₂O)₂(H₂W₁₂O₄₂)]·24H₂O (3), were synthesized and characterized by elemental and thermogravimetric (TG)analysis, infrared spectroscopy and X-ray single-crystal analysis. Both complexes 1 and 2 exhibit one-dimensional structure with two neighboring paradodecatungstate-B clusters, [H₂W₁₂O₄₂]¹⁰⁻, linked by [Cu(H₂O)₂]²⁺ or [Cd(H₂O)₂]²⁺ units, while complex 3 displays a two-dimensional network structure. The electrochemical behaviors of complexes 1 and 3 were investigated in the buffer solution of pH 4.8. The results of electrocatalysis reveal that the reduced species of complexes 1 and 3 are electrocatalytically active for the reduction of nitrite. Complex 1 exhibits the electrocatalytic activity for the reduction of nitrate as well. The surface photovoltage spectroscopy (SPS) and electric field-induced SPS (EFISPS) measurements show that the surface photovoltage behavior of complex 1 is complicated while complex 3 bears the property of n-type semiconductor.     

Potentiometric and spectroscopic studies of three new mixed inorganic–organic hybrid materials based on Preyssler and Wells–Dawson heteropolyoxometalates containing proline, leucine, and asparagine

Three new organic–inorganic hybrid materials based on two important heteropolyoxometalates namely Preyssler (=K_12.5H_1.5[Na(H₂O)P₅W₃₀O₁₁₀]·35H₂O) and Wells–Dawson (=K₆[P₂W₁₈O₆₂]·10H₂O) anions, namely, (Hpro)₉(Hleu)₃K₂[Na(H₂O)P₅W₃₀O₁₁₀]·25H₂O (1), (Hpro)₄(Hasp)[HP₂W₁₈O₆₂]·20H₂O (2), and (Hpro)₁₁K₃[Na(H₂O)P₅W₃₀O₁₁₀]·18H₂O (3) where pro, leu, and asp are proline, leucine, and asparagine, respectively, were prepared and identified by elemental analysis, infrared and proton nuclear magnetic resonance spectroscopies, and thermogravimetric analysis. The hybrid materials are made up of positively charged amino acids, [Na(H₂O)P₅W₃₀O₁₁₀]^14? and [P₂W₁₈O₆₂]^6? anions, and H₂O molecules of crystallization. These constituents’ fragments held together into a three-dimensional supermolecular network through non-covalent interactions. The protonation constants of the amino acids used, and Preyssler and Wells–Dawson species in all possible protonated forms, the equilibrium constants for binary systems of proline–asparagine and proline–leucine, and the stoichiometry and stability constants of the corresponding binary and ternary hybrids with Preyssler and Wells–Dawson heteropolyoxometalates in aqueous solution were investigated by potentiometric pH titration method. The stoichiometries of the most hybrid species in solution were compared with the corresponding hybrids in the solid phase, in detail.     

Synthesis and Disassembly/Reassembly of Giant Ring‐Shaped Polyoxotungstate Oligomers

The disassembly and reassembly of giant molecules are essential processes in controlling the structure and function of biological and artificial systems. In this work, the disassembly and reassembly of a giant ring‐shaped polyoxometalate (POM) without isomerization of the monomeric units is reported. The reaction of a hexavacant lacunary POM that is soluble in organic solvents, [P₂W₁₂O₄₈]^14?, with manganese cations gave the giant ring‐shaped POM [{γ‐P₂W₁₂O₄₈Mn₄(C₅H₇O₂)₂(CH₃CO₂)}₆]^42?. This POM is a hexamer of manganese‐substituted {P₂W₁₂O₄₈Mn₄} units, and its inner cavity was larger than any of those previously reported for ring‐shaped polyoxotungstates. It was disassembled into monomeric units in acetonitrile, and the removal of the capping organic ligands on the manganese cations led to reassembly into a tetrameric ring‐shaped POM, [{γ‐P₂W₁₂O₄₈Mn₄(H₂O)₆}₄(H₂O)₄]^24?.     

Trigonal Prismatic Coordination of Discrete Rare Earth Ions,Enforced by the Polyoxotungstate [P4W27O99(H2O)]16–

A family of solution-stable polyanions [Na⊂{Ln^III(H₂O)}{W^VIO(H₂O)}P^V₄W^VI₂₆O₉₈]¹²⁻ (Ln=Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y) represent the first examples of polyoxometalates comprising a single lanthanide(III) or yttrium(III) ion in a rare trigonal prismatic O₆ environment. Their synthesis exploits the reactivity of the organophosphonate-functionalized precursor [P₄W₂₄O₉₂(C₆H₅P^VO)₂]¹⁶⁻ with heterometal ions and yields hydrated potassium or mixed lithium/potassium salts of composition K_xLn_yH_12–x–y[Na⊂{Ln(H₂O)}{WO(H₂O)}P₄W₂₆O₉₈]⋅nH₂O⋅mLiCl (x=8.5–11; y=0–2; n=24–34; m=0–1.5). The Dy, Ho, Er and Yb derivatives are characterized by slow magnetization relaxation.     

A series of new supramolecular structures constructed from triethylenediamine and different polyoxometalates

Three new supramolecular compounds based on triethylenediamine and different polyoxometalates [W^VI₃V^V₃O₁₉H]{[Cu(HDABCO)]₂(H₂O)} (1), [P₂Mo^VI₁₈O₆₂][HDABCO]₂[H₂DABCO]₂·12 H₂O (2) and [Mo^VI_7.5W^VI_0.5O₂₇][Cu(HDABCO)]₂·2 H₃O·2 H₂O (3) (DABCO=triethylenediamine) have been synthesized hydrothermally and characterized by IR, TG, XPS and X-ray diffraction analyses. Crystal structure analyses reveal that compound 1 exhibits a face-centered cubic packing motif, compound 2 displays a supramolecular structure constructed form the “chains” arranged hexagonally, compound 3 contains [Mo_7.5W_0.5O₂₇]_∞ chain decorated by [Cu(HDABCO)]²⁺ cations, which was then packed into a layer structure. These results show that the same organonitrogen combining with the different POMs will yield different supramolecular networks.     

Two New {P<Subscript>8</Subscript>W<Subscript>49</Subscript>} Wheel-shaped Tungstophosphates Decorated by Co(II), Ni(II) Ions

Two new wheel-shaped tungstophosphates based on 3d-transition metals (Co(II), Ni(II)) ions decorated [P₈W₄₉O₁₈₇]⁴⁰⁻ anion (TM-{P₈W₄₉}), K₄Na₂₂{[Co(H₂O)₂Cl][Co(H₂O)₃]₂[Co(H₂O)₅]_1.5 [Co(H₂O)₃H₄P₈W₄₉O₁₈₇(H₂O)]}·2NaCl·41·5H₂O 1 and Na₃₀{[Ni(H₂O)₃]₂[{Ni(H₂O)₃}_1.5H₃P₈W₄₉O₁₈₇ (H₂O)]}·41.5H₂O 2 have been synthesized by routine synthetic reaction of hexavacant Dawson polyoxonanion [P₂W₁₂O₄₈]¹⁴⁻ with divalent 3d transition-metal ions in aqueous solution. The two compounds are characterized by elemental analysis, IR spectroscopy, TG analysis, electrochemical analysis, and single-crystal X-ray diffraction. Both compounds contain a 2D layer-like structure constructed from 1D chains of wheel-type [P₈W₄₉O₁₈₇]⁴⁰⁻ anions bridged via CoO₆ or NiO₆ units. Cyclic voltammograms and ³¹P NMR analysis suggest that the polyanion [P₈W₄₉O₁₈₇]⁴⁰⁻ of both compounds are stable in aqueous solution (pH = 4).