Stabilization of uranium(IV) in heteropoly anions*

Summary The heteropoly anions [U^IVMo₁₂O₄₂]^8–(UMo₁₂), [U^IVW₁₀O₃₆]^8– (UW₁₀), [U^IV(PW₁₁O₃₉)₂]¹⁰ [U(PW₁₁)₂] and [U^IV(SiW₁₁O₃₉)₂]¹² [U(SiW₁₁)₂] were examined by cyclic voltammetry on a wax-impregnated carbon electrode. Reversible one-electron oxidations were observed for UMo₁₂ (E = +0.91 V vs see at pH = ca. 0), U(PW₁₁ )2 (E = +0.60 V at pH 4.4) and U(SiW₁₁)₂ (E = +0.19 V at pH 4.4). No oxidation of UW₁₀ was detected at potentials prior to oxygen discharge (ca. +0.9 V at pH 7). Controlled potential oxidation of aqueous solutions of UMo₁₂ gave unstable solutions of [U^VMo₁₂O₄₂]^7–. Oxidation of U(PW₁₁)2 was achieved in aqueous and nonaqueous (acetonitrile, propylene carbonate) solution. The electronic spectra of U^VMo₁₂ and U^V(PW₁₁)₂ are reported and are discussed in terms of UO₁₂ (/y) and UO₈ (D4d) chromophores respectively. Possibilities for geometrical and optical isomers of U(XW 11)2 anions are considered. Solutions of brucinium salts of U(PWI I)2 and UW₁₀ in dimethyl formamide show induced Cotton effects at wavelengths corresponding to the f-f transitions of UIV. The voltammograms of UMo₁₂, ThMo₁₂ and CeMo₁₂ show an irreversible twelve-electron reduction at -0.25 V. The pale brown reduced solutions cannot be reoxidized to the original heteropoly anions.Taken from the Ph. D. Thesis of S.C.T., Georgetown University, 1977. Presented in part at the 17th International Conference on Coordination Chemistry, Hamburg, September 1976.     

Investigation of inorganic–organic hybrid materials containing polyoxometalate cluster anions and organic dye cations

Two new ionic-pair salts containing an organic dye cation, i.e. New Fuchsin or Pararosaniline cation, with Keggin-type POMs, [SiW₁₂O₄₀]^4? and [BW₁₂O₄₀]^6?, have been isolated under hydrothermal conditions. [(C₂₂H₂₄N₃)₄][SiW₁₂O₄₀] (1) and [(C₁₉H₁₈N₃)₆][BW₁₂O₄₀] (2) have been characterized by elemental analyses, FT-IR and single crystal X-ray crystallography. Both of these complexes have strong absorption in the visible-light range due to the involvement of the organic dye and both show weak fluorescence emission.     

Differential pulse voltammetric determination of P(V) following adsorptive accumulation of alpha-[PMo(12)O(40)](3-) on a polypyrrole-modified glassy carbon electrode

On the basis of the formation and pre-concentration of an α-Keggin-type [PMo₁₂O₄₀]³⁻ complex, a novel voltammetric method was developed for the determination of trace levels of P(V). The α-[PMo₁₂O₄₀]³⁻ complex was formed by heating a 5×10⁻⁴ M Mo(VI)-0.2 M HCl-40% (v/v) CH₃CN system containing a trace amount of P(V) at 70 °C for 30 min. During the electrochemical polymerization of pyrrole in the α-[PMo₁₂O₄₀]³⁻ solution, the α-[PMo₁₂O₄₀]³⁻ complex was accumulated into the polypyrrole film on a glassy carbon electrode. The differential pulse voltammetric peak current due to the α-[PMo₁₂O₄₀]³⁻ complex incorporated in the polypyrrole film was linearly dependent on the P(V) concentration in the range of 5×10⁻⁹-5×10⁻⁷ M; a detection limit of 2×10⁻⁹ M was achieved.     

Activation-controlled outer-sphere electron transfer reactions: reduction of heteropoly 11-tungstovanadophosphate and heteropoly 10-tungstodivanado phosphate by thiourea in aqueous acid medium

The kinetics of reduction of heteropoly 11-tungstovanadophosphate, [PV^VW₁₁O₄₀]⁴⁻, (HPA1) and heteropoly 10-tungstodivanadophosphate, [PV^VV^VW₁₀O₄₀]⁵⁻, (HPA2) by thiourea has been investigated in HClO₄/phthalate/acetate buffer solutions spectrophotometrically at 25 °C in aqueous medium. The stoichiometry of the reaction is 1:1 in both cases. The HPAs are converted into the corresponding one-electron reduced heteropoly blues, namely, [PV^IVW₁₁O₄₀]⁵⁻ and [PV^IVV^VW₁₀O₄₀]⁶⁻, and thiourea is oxidised to formamidine disulphide. The reaction shows first-order dependence in both [HPA] and [thiourea] at constant pH. The rate–pH profile shows the participation of both the neutral and deprotonated forms of thiourea in the reaction. The reaction proceeds through an outer sphere electron transfer mechanism in which activation-controlled electron transfer is the rate-determining step. Self-exchange rate constants for the couples [PV^VW₁₁O₄₀]⁴⁻/[PV^IVW₁₁O₄₀]⁵⁻, [PV^VV^VW₁₀O₄₀]⁵⁻/[PV^IVV^VW₁₀O₄₀]⁶⁻ and H₂NCSNH₂/H₂NCS^·+NH₂ have been evaluated by Marcus theory.     

Layer-by-layer assembly of multilayer films of polyoxometalates and tris(phenanthrolinedione) complexes of transition metals

A series of organic-inorganic composite films were prepared by the layer-by-layer self-assembly method containing the phendione complexes of transition metals [M(phendione)₃]²⁺ (M=Fe²⁺, Co²⁺, phendione=1,10-phenanthroline-5,6-dione) and the polyoxometalates (POMs). UV-vis spectroscopy was used to follow the fabrication process of (BW₁₂/[M(phendione)₃]²⁺)_n (BW₁₂=BW₁₂O₄₀⁵⁻, M=Fe²⁺, Co²⁺) and (Co₄(PW₉)₂/[M(phendione)₃]²⁺)_n (Co₄(PW₉)₂=Co₄(H₂O)₂(PW₉O₃₄)₂¹⁰⁻, M=Fe²⁺, Co²⁺) multilayer films. Electrochemical studies on the films illustrate that the POM species exhibit well-defined redox peaks and the phendione species show pH-dependent electrochemical behavior. The photoluminescent properties were investigated to show the (BW₁₂/[Fe(phendione)₃]²⁺)_n film with low-energey red photoluminescence at 672 nm.     

Two one-dimensional mono-substituted heteropolytungstates based on Keggin anion units

Two kinds of complexes [Ni(DETA)₂]₃[SiNiW₁₁O₃₉]·2.5H₂O (DETA=diethylenetriamine) (1) and [H₂en]₂[Ba_0.15(H₂O)₂(Hen₂)]H_1.7[SiNaW₁₁O₃₉]·2H₂O (2) were obtained from the hydrothermal reaction and characterized by single crystal X-ray diffraction analysis and IR spectra. Crystal data: C₂₄H₈₃N₁₈Ni₄O_41.5SiW₁₁ (1), monoclinic, Pn, a=10.926(2) Å, b=23.022(5) Å, c=13.221(3) Å, β=94.27(3)°, V=3316.4(11) Å³, Z=2; C₈H_46.7N₈Ba_0.15NaO₄₃SiW₁₁ (2), monoclinic, P2₁, a=12.840(3) Å, b=11.174(2) Å, c=16.693(3) Å, β=91.14(3)°, V=2394.4(8) Å³, Z=2. Both of them consists of one mono-substituted Keggin unit [SiMW₁₁O₃₉]⁽⁸⁻ⁿ⁾⁻ (MNi, Na, n=2, 1) obtained by metal atom substituting for a W atom from the plenary anion [SiW₁₂O₄₀]⁴⁻. This unit then connects with other adjacent units via M-O-W bridges constructing an infinitely one-dimensional chain-like structure in which the metal cation and polyanion alternate. Moreover, both of Ni or Na atoms are in a distorted octahedral environment with six oxygen atoms and occupy one position in the oxometalate shell of the Keggin structure.     

Syntheses, structures and properties of 3D inorganic-organic hybrid frameworks constructed from lanthanide polymer and Keggin-type tungstosilicate

Inorganic-organic hybrid frameworks, namely [Ce(H₂O)₃(pdc)]₄[SiW₁₂O₄₀]·6H₂O 1, [M(H₂O)₄(pdc)]₄[SiW₁₂O₄₀]·2H₂O (M=Ce for 2a, La for 2b, Nd for 2c; H₂pdc=pyridine-2,6-dicarboxylic acid) were assembled through incorporation of Keggin-type heteropolyanion [SiW₁₂O₄₀]⁴⁻ within the voids of lanthanides-pdc network as pillars or guests under hydrothermal condition. Single-crystal X-ray analyses of these crystals reveal that compound 1 presents 3D pillar-layered framework with the [SiW₁₂O₄₀]⁴⁻ anions located on the square voids of the two-dimensional Ce-pdc bilayer. Compounds 2a-c are isostructural and constructed from 3D Ln-pdc-based metal-organic framework (MOF) incorporating noncoordinating guests Keggin structure [SiW₁₂O₄₀]⁴⁻. Solid-state properties of compounds 1 and 2a-c such as thermal stability and photoluminescence have been further investigated.     

High‐Field Pulsed EPR Spectroscopy for the Speciation of the Reduced [PV2Mo10O40]6− Polyoxometalate Catalyst Used in Electron‐Transfer Oxidations

An in‐depth spectroscopic EPR investigation of a key intermediate, formally notated as [PV^IVV^VMo₁₀O₄₀]^6? and formed in known electron‐transfer and electron‐transfer/oxygen‐transfer reactions catalyzed by H₅PV₂Mo₁₀O₄₀, has been carried out. Pulsed EPR spectroscopy have been utilized: specifically, W‐band electron–electron double resonance (ELDOR)‐detected NMR and two‐dimensional (2D) hyperfine sub‐level correlation (HYSCORE) measurements, which resolved ⁹⁵Mo and ¹⁷O hyperfine interactions, and electron–nuclear double resonance (ENDOR), which gave the weak ⁵¹V and ³¹P interactions. In this way, two paramagnetic species related to [PV^IVV^VMo₁₀O₄₀]^6? were identified. The first species (30–35 %) has a vanadyl (VO²⁺)‐like EPR spectrum and is not situated within the polyoxometalate cluster. Here the VO²⁺ was suggested to be supported on the Keggin cluster and can be represented as an ion pair, [PV^VMo₁₀O₃₉]^8?[V^IVO²⁺]. This species originates from the parent H₅PV₂Mo₁₀O₄₀ in which the vanadium atoms are nearest neighbors and it is suggested that this isomer is more likely to be reactive in electron‐transfer/oxygen‐transfer reaction oxidation reactions. In the second (70–65 %) species, the V^IV remains embedded within the polyoxometalate framework and originates from reduction of distal H₅PV₂Mo₁₀O₄₀ isomers to yield an intact cluster, [PV^IVV^VMo₁₀O₄₀]^6?.     

Synthesis,structures and electrochemical properties of four organic–inorganic hybrid polyoxometalates constructed from polyoxotungstate clusters and transition metal complexes

Four novel organic–inorganic hybrid compounds [Cu₅ ^I(4,4′-bpy)₃(2,2′-bpy)₄][BW₁₂O₄₀] · H₂O (1), [Ni_0.5(2,2′-bpy)_1.25][Ni(2,2′-bpy)₃][Ni(2,2′-bpy)₂(H₂O)(SiW₁₁^VIW^VO₄₀)] · 0.5H₂O (2), [H₂bpy]₂[Zn(2,2′-bpy)₃]₂[Si₂W₁₈O₆₂] · 1.5H₂O (3) and [Cu^II(2,2′-bpy)₂]₂[SiW₁₂O₄₀] · 2H₂O (4) (2,2′-bpy = 2,2′-bipyridine, 4,4′-bpy = 4,4′-bipyridine) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, electrochemical measurements and single-crystal X-ray diffraction. Compound (1) is a novel [BW₁₂O₄₀]⁵⁻ polyoxoanion bisupported by copper(I) coordination cations with mixed 2,2′-bpy and 4,4′-bpy ligands. Compound (2) is constructed from the [SiW₁₁^VIW^VO₄₀]⁵⁻ polyoxoanions supported by [Ni(2,2′–bpy)₂]²⁺. Compound (3) is composed of a novel [Si₂W₁₈O₆₂]⁸⁻ cluster and [Zn(2,2′–bpy)₃]²⁺ complexes, which held together into a three-dimensional (3D) supramolecular network through hydrogen-bonding interactions. Compound (4) shows a 2D layer framework constructed from a bisupporting Keggin polyoxoanion cluster and [Cu(2,2′–bpy)₂]²⁺ coordination polymer fragments, resulting in 3D networks via supramolecular interactions. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Hydrothermal Synthesis and Characterization of (H3N(CH2)4NH3)[V6O14]

A new layered vanadium oxide [H₃N(CH₂)₄NH₃](V₆O₁₄) was synthesized hydrothermally under autogenous pressure at 180°C for 48 h from a mixture of H₂N(CH₂)₄NH₂ and V₂O₅ in aqueous solution. Its structure was determined from single-crystal X-ray diffraction at room temperature with final R=0.0774 and R_w=0.0893. It crystallizes in the monoclinic system (space group P2₁/n with a=9.74(2) Å, b=6.776(5) Å, c=12.60(2) Å, β=96.1(1)°, V=827(2) ų and Z=2). This compound contains mixed-valence V⁵⁺/V⁴⁺ vanadium oxide layers built from [V^VO₄] tetrahedra and pairs of edge-sharing [V^IVO₅] square pyramids with protonated organic amines occupying the interlayer space.     

One-step synthesis and stabilization of gold nanoparticles and multilayer film assembly

Au nanoparticles (NPs) were synthesized in the one-pot procedure in water at room temperature with the wheel-shaped V^V-V^IV mixed-valence tungstovanadate [P₈W₄₈O₁₈₄{V₄^VV₂^IVO₁₂(H₂O)₂}₂]³²⁻ (V12) acting as both reducing and stabilizing agents. The V12 stabilized Au NPs (Au@V12 NPs) were characterized by SEM, TEM, DLS, UV-vis spectroscopy, XPS, and XRD analyses and the negatively charged surface of the Au@V12 NPs was proved by the zeta potential analysis. Based on the layer-by-layer assembly (LbL), the Au@V12 NPs-containing multilayer films have been fabricated on ITO-coated glass slide and quartz substrates with poly(ethyleneimine) (PEI). The regular growth of the multilayer films was monitored by UV-vis spectroscopy and cyclic voltammetry, the composition was characterized by XPS. The Au@V12 NPs based composite films showed electrocatalytic activities towards the reduction of dioxygen and the oxidation of methanol. This approach is expected to open the way towards procedures aimed at the one-step fabrication of Au NPs and polyoxometalates (POMs) into the multilayer films.     

Exchange coupling in alkoxy-polyoxovanadates [VIVnVV6?nO7(OR)12]4?n (n = 4, 3, 2)

The molecular structure and magnetic properties of alkoxy-polyoxovanadates [V^IV _n V^V _6−n O₇(OR)₁₂]⁴⁻ⁿ (n = 4, 3, 2) were studied within the framework of the DFT approach. The equilibrium geometric configurations of all complexes studied in this work are characterized by a distorted octahedral hexavanadate core; the unpaired d-electrons are localized on the metal centers (V^IV). The localized spin density distribution is also retained in the low-temperature crystal structures of the compounds whose magnetic properties are described by the Heisenberg-Dirac-van Vleck exchange spin Hamiltonian. The exchange parameters calculated using the broken symmetry formalism suggest predominance of ferromagnetic coupling between vanadium(IV) ions in the μ-OR bridged dimeric units {V^IVO(OR)V^IV} and in the diagonal pairs {V^IVOV^IV} (n = 4). The results obtained indicate that the magnitude and sign of the exchange parameters in the isostructural dimeric units within the hexavanadate core depend on the total number of unpaired electrons in the system.     

Synthesis,properties and photochromism of novel charge transfer compounds with Keggin anions and protonated 2,2′-biquinoline

Several novel compounds with protonated 2,2′-biquinoline (biqui) and Keggin polyoxoanions (α-isomers), having the general formula (Hbiqui)_m[XM₁₂O₄₀]·nsolv, X=P (m=3), Si (m=4); M=Mo, W; n=0, 3; solv=H₂O, N,N-dimethylformamide (dmf), were synthesized and characterized by analytical, spectroscopic and X-ray diffraction techniques. Electronic spectroscopy (visible/UV) indicated the presence of intermolecular charge transfer between the organic and inorganic moieties in the solid state. Evidence for the existence of intermolecular electronic interaction in solution was found for compounds with the [SiW₁₂O₄₀]⁴⁻ anion, a fact quite uncommon for charge transfer compounds based on Keggin anions. A single crystal X-ray diffraction study could be performed on (Hbiqui)₄[SiW₁₂O₄₀]·3dmf crystals, but the refinements revealed the presence of highly disordered 2,2′-biquinoline molecules and α-[SiW₁₂O₄₀]⁴⁻ anions. Photosensitivity to sunlight and to W-lamp visible light was assessed for all compounds. Photochromic properties were found for solids with [XMo₁₂O₄₀]^m− Keggin anions. Reduction of these anions upon irradiation was observed by diffuse reflectance and EPR spectroscopy. After a minimum of 5 h under sunlight, the extent of anion reduction followed the order (Hbiqui)₃[PMo₁₂O₄₀]·3dmf>(Hbiqui)₄[SiMo₁₂O₄₀]·3dmf>(Hbiqui)₃[PMo₁₂O₄₀]>(Hbiqui)₄[SiMo₁₂O₄₀]·4H₂O. The Kurtz powder test was used to evaluate the second-order non-linear optical properties of the prepared compounds. (Hbiqui)₄[SiW₁₂O₄₀]·3H₂O originated a second harmonic generation signal with intensity about 15% that of urea for 1064 nm radiation.     

Vanadium (IV) porphyrins: synthesis and spectro-chemical characterization of thiovanadyl porphyrins. Exafs structural study of thio (2, 3, 7, 8, 12, 13, 17, 18 - octaethylporphyrinato) vanadium (IV).

The action of elemental sulfur with vanadium (II) porphyrins complexes [V^II(por)(THF)₂] (por = porphyrinate) affords the thiovanadyl porphyrins [V^IV(por)(S)]. EXAFS spectroscopy at the V K-edge of [V^IV(oep)(S)] confirms the axial symmetry of these complexes.     

Synthesis,structural characterization and catalytic potential of oxidovanadium(IV) and dioxidovanadium(V) complexes with thiazole-derived NNN-donor ligand

Reaction between the tridentate NNN donor ligand, (E)-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)benzo[d]thiazole (HL), and V₂O₅ in ethanol gave a new vanadium(V) complex, [VO₂L] (1), while the similar reaction by using [V^IVO(acac)₂] as the metal source gave two different types of crystals related to compounds [VO₂L] (1) and [V^IVO(acac)L] (2). The molecular structures of the complexes were determined by single-crystal X-ray diffraction and spectroscopic characterization was carried out by means of FT-IR, UV–vis and NMR experiments as well as elemental analysis. The oxidovanadium(IV) and dioxidovanadium(V) species were used as catalyst precursors for olefin oxidation in the presence of hydrogen peroxide (H₂O₂) as an oxidant. Under similar experimental conditions, the presence of 1 resulted in higher oxidation conversion than 2.     

Two supramolecular structures constructed from Keggin-type polyoxometalates and 4,4′-bipyridine

Two supramolecular compounds based on Keggin-type polyoxometalates (POMs), (4,4′-H₂bpy)(4,4′-Hbpy)[PMo₁₂O₄₀] (1) and (4,4′-H₂bpy)(4,4′-Hbpy)₂[SiW₁₂O₄₀]?·?4H₂O (2), have been synthesized hydrothermally and characterized by elemental analyses, IR, UV-Vis, XPS spectra, thermogravimetric analyses, and single-crystal X-ray diffraction analyses. The two compounds consist of 4,4′-bipyridine (4,4′-bpy) ligands and different Keggin-type POMs which are [PMo₁₂O₄₀]^3? for 1 and [SiW₁₂O₄₀]^4? for 2. There are hydrogen-bonding interactions between the POMs, 4,4′-bipyridine, and/or water in 1 and 2. In addition, 2 contains an uncommon (H₂O)₂ water cluster.     

A new organic-inorganic hybrid material constructed from Keggin polyanion and transition metal complexes: [Co(2,2′-bipy)3]1.5[SiWVWVI 11O40Co(2,2′-bipy)2(H2O)] · 0.5H2O

A new organic-inorganic hybrid compound constructed from Keggin-type polyanion clusters and transition metal complexes, [Co(2,2′-bipy)₃]_1.5[SiW^VW^VI ₁₁O₄₀Co(2,2′-bipy)₂(H₂O)] ·?0.5H₂O (1), has been hydrothermally prepared and characterized by elemental analysis, IR, UV–Vis, TG-DTA and single crystal X-ray diffraction. Compound 1 crystallized in the monoclinic system, space group C2/c, a =?46.995(15), b =?14.487(5), c =?26.205(9)Å, β =?90.000(0)°, V =?17841(10)ų, Z =?4. Compound 1 contains a [SiW^VW^VI ₁₁O₄₀Co(2,2′-bipy)₂(H₂O)]^3? polyoxoanion in which [Co(2,2′-bipy)₂(H₂O)]²⁺ is covalently bonded to the α-Keggin-type heteropolyanion [SiW^VW^VI ₁₁O₄₀]^5? via a terminal oxygen.     

Peroxide derivatives of heteropoly compounds with Keggin anions [PW<Subscript>12</Subscript>O<Subscript>40</Subscript>]<Superscript>3−</Superscript> and [SiW<Subscript>12</Subscript>O<Subscript>40</Subscript>]<Superscript>4−</Superscript>: Synthesis and structure

Peroxide derivatives of heteropoly compounds with Keggin anions [PW₁₂O₄₀]^3? and [SiW₁₂O₄₀]^4? are isolated in an individual state from concentrated hydrogen peroxide solutions and characterized by physicochemical methods. The structure of Ba₂[SiW₁₂O₄₀] · 4H₂O₂ · 11H₂O (I) is solved by X-ray crystallography. Crystals of compound I (H₃₀Ba₂O₅₉Si₁W₁₂, FW = 3483.21) are monoclinic, space group C2/c, a = 24.981(2) Å, b = 12.2103(11) Å, c = 18.7142(17) Å, β = 122.620(2)^o, V = 4808.0(8) ų, Z = 4. The structure contains Keggin anions [SiW₁₂O₄₀]^4?; all hydrogen peroxide molecules are coordinated to Ba²⁺ cations.     

Hydrothermal Synthesis and Crystal Structure of a New a-Keggin Unit-supported Cobalt Bipyridyl Complex: [Co(2,2'-BIPY)3]1.5[SiW12O40Co(2,2'-bipy)2(H2O)]·0.5H2O

A new α-Keggin unit-supported transition metal complex [Co(2,2′-bipy)₃]_1.5[SiW₁₂O₄₀Co(2,2′-bipy)₂-(H₂O)]·0.5H₂O has been hydrothermally synthesized and characterized by X-ray crystallography, showing that [Co(2,2′-bipy)₂(H₂O)]²⁺ units are covalently bonded to the α-Keggin cluster [SiW^VW^VI ₁₁O₅₀]^5?. Intermolecular hydrogen bonding interactions and short O … O contacts force the structure into an interesting one-dimensional supramolecular array. Crystals are monoclinic space group C2/c, with a = 46.676(9), b = 14.348(3), c = 26.010(5) Å, β = 90.33(3)°, V = 17419(6) ų, Z = 8.     

Polyoxometalate immobilization in Cu/Ag-pz porous coordination polymers: The influences of them on the structural properties of frameworks

Three new high dimensional Cu^I/Ag-pz porous coordination polymers (PCPs) with different Keggin polyoxometalate templates have been hydrothermally synthesized: [Cu^I₅(pz)₆Cl][HPMo^VI₁₀Mo^V₂O₄₀] (1) [Ag₅(pz)₇(BW₁₂O₄₀)] (2) and [Cu^I₅(pz)₆H(H₂W₁₂O₄₀)]·4H₂O (3) (pz=pyrazine). The choice of the particular Keggin POM templates is shown to influence the structural properties of the Cu/Ag PCPs. Compound 1 shows a Cl-bridged Cu-pz-Cl double layer, between which two kinds of [HPMo^VI₁₀Mo^V₂O₄₀]⁴⁻(PMo₁₂) polyanions are located. Compound 2 presents a 3D Ag-pz framework with parallelogram-like voids, into which BW₁₂O₄₀⁵⁻ (BW₁₂) Keggin ions are incorporated. Compound 3 contains a Cu-pz cationic layer framework, between which are located [H(H₂W₁₂O₄₀)]⁵⁻ (W₁₂) Keggin ions. Primary photocatalytic experiment indicates that compound 1 presents excellent photocatalytic activity. The photoluminescence properties and electrochemistry properties of the compounds are also discussed.