Polyoxometalates (POMs) are discrete anionic metaloxygen clusters which can be regarded as soluble oxide fragments. They exhibit a great diversity of sizes, nuclearities, and shapes. They are built from the connection of {MOx} polyhedra, M being a d-block element in high oxidation state, usually VIV,V, MoVI, or WVI.1 While these species have been known for almost two centuries, they still attract much interest partly based on their large domains of applications. They play a great role in various areas ranging from catalysis,2 medicine,3 electrochemistry,4 photochromism,5 to magnetism.6 This palette of applications is intrinsically due to the combination of their added value properties (redox properties, large sizes, high negative charges, nucleophilicity...). Parallel to this domain, the organic-inorganic hybrids area has followed a similar expansion during the last 10 years. The concept of organic-inorganic hybrid materials * To whom correspondence should be addressed. E-mail: dolbecq@ chimie.uvsq.fr. Chem. Rev. 2010, 110, 6009–6048 6009

Hybrid Organic−Inorganic Polyoxometalate Compounds: From Structural Diversity to Applications

Polyoxometalates (POMs) represent an important group of metal-oxo nanoclusters, typically comprised of early transition metals in high oxidation states (mainly V, Mo and W). Many plenary POMs exhibit good pH, solvent, thermal and redox stability, which makes them attractive components for the design of covalently integrated hybrid organic-inorganic molecules, herein referred to as hybrid-POMs. Until now, thousands of organic hybrid-POMs have been reported; however, only a small fraction can be further functionalized using other organic molecules or metal cations. This emerging class of 'post-functionalizable' hybrid-POMs constitute a valuable modular platform that permits coupling of POM properties with different organic and metal cation functionalities, thereby expanding the key physicochemical properties that are relevant for application in (photo)catalysis, bioinorganic chemistry and materials science. The post-functionalizable hybrid-POM platforms offer an opportunity to covalently link multi-electron redox responsive POM cores with virtually any (bio)organic molecule or metal cation, generating a wide range of materials with tailored properties. Over the past few years, these materials have been showcased in the preparation of framework materials, functional surfaces, surfactants, homogeneous and heterogeneous catalysts and light harvesting materials, among others. This review article provides an overview on the state of the art in POM post-functionalization and highlights the key design and structural features that permit the discovery of new hybrid-POM platforms. In doing so, we aim to make the subject more comprehensible, both for chemists and for scientists with different materials science backgrounds interested in the applications of hybrid (POM) materials. The review article goes beyond the realms of polyoxometalate chemistry and encompasses emerging research domains such as reticular materials, surfactants, surface functionalization, light harvesting materials, non-linear optics, charge storing materials, and homogeneous acid-base catalysis among others.

Hybrid polyoxometalates as post-functionalization platforms: from fundamentals to emerging applications

Polyoxometalates containing late transition and noble metal atoms

III.8.1. Oxo Ligands 60 III.8.2. Mixed-Ligand Compounds 61 III.9. Sulfur-Containing Compounds 62 III.10. Host−Guest Compounds 63 IV. Heteropolyanions 64 IV.1. The Keggin Structure and Its Isomers 64 IV.2. Reduced Compounds 66 IV.3. Mixed-Metal Heteropolyanions 66 IV.4. Compounds with One Vacant Metal Site 67 IV.5. Compounds with Three Vacant Metal Sites 68 IV.6. Three Vacant Metal Site Heteropolyanions with Mixed Ligands 69

http://www1.udel.edu/chem/polenova/PDF/Polyoxometalates/POM_nomenclature_ChemRev1998.pdf

The Nomenclature of Polyoxometalates: How To Connect a Name and a Structure†

Five Co(II) silicotungstate complexes are reported. The centrosymmetric heptanuclear compound K(20)[{(B-beta-SiW(9)O(33)(OH))(beta-SiW(8)O(29)(OH)(2))Co(3)(H(2)O)}(2)Co(H(2)O)(2)]47 H(2)O (1) consists of two {(B-beta-SiW(9)O(33)(OH))(beta-SiW(8)O(29)(OH)(2))Co(3)(H(2)O)} units connected by a {CoO(4)(H(2)O)(2)} group. In the chiral species K(7)[Co(1.5)(H(2)O)(7))][(gamma-SiW(10)O(36))(beta-SiW(8)O(30)(OH))Co(4)(OH)(H(2)O)(7)]36 H(2)O (2), a {gamma-SiW(10)O(36)} and a {beta-SiW(8)O(30)(OH)} unit enclose a mononuclear {CoO(4)(H(2)O)(2)} group and a {Co(3)O(7)(OH)(H(2)O)(5)} fragment. The two trinuclear Co(II) clusters present in 1 enclose a mu(4)-O atom, while in 2 a mu(3)-OH bridging group connects the three paramagnetic centers of the trinuclear unit, inducing significantly larger Co-L-Co (L=mu(4)-O (1), mu(3)-OH (2)) bridging angles in 2 (theta(av(Co-L-Co))=99.1 degrees ) than in 1 (theta(av(Co-L-Co))=92.8 degrees ). Weaker ferromagnetic interactions were found in 2 than in 1, in agreement with larger Co-L-Co angles in 2. The electrochemistry of 1 was studied in detail. The two chemically reversible redox couples observed in the positive potential domain were attributed to the redox processes of Co(II) centers, and indicated that two types of Co(II) centers in the structure were oxidized in separate waves. Redox activity of the seventh Co(II) center was not detected. Preliminary experiments indicated that 1 catalyzes the reduction of nitrite and NO. Remarkably, a reversible interaction exists with NO or related species. The hybrid tetranuclear complexes K(5)Na(3)[(A-alpha-SiW(9)O(34))Co(4)(OH)(3)(CH(3)COO)(3)]18 H(2)O (3) and K(5)Na(3)[(A-alpha-SiW(9)O(34))Co(4)(OH)(N(3))(2)(CH(3)COO)(3)]18 H(2)O (4) were characterized: in both, a tetrahedral {Co(4)(L(1))(L(2))(2)(CH(3)COO)(3)} (3: L(1)=L(2)=OH; 4: L(1)=OH, L(2)=N(3)) unit capped the [A-alpha-SiW(9)O(34)](10-) trivacant polyanion. The octanuclear complex K(8)Na(8)[(A-alpha-SiW(9)O(34))(2)Co(8)(OH)(6)(H(2)O)(2)(CO(3))(3)]52 H(2)O (5), containing two {Co(4)O(9)(OH)(3)(H(2)O)} units, was also obtained. Compounds 2, 3, 4, and 5 were less stable than 1, but their partial electrochemical characterization was possible; the electronic effect expected for 3 and 4 was observed.

Effect of Cyanato, Azido, Carboxylato, and Carbonato Ligands on the Formation of Cobalt(II) Polyoxometalates: Characterization, Magnetic, and Electrochemical Studies of Multinuclear Cobalt Clusters

Hydrothermal reaction of lacunary [(PO4)W11O35]7- with rhodium acetate dimer yields the novel dirhodium-substituted Keggin anion, [(PO4)W11O35{Rh2(OAc)2}]5- (1) An X-ray structure determination of the guanidiunium salt of the dimethyl sulfoxide derivative of 1 confirms the structure deduced from proton and tungsten NMR spectroscopy Oxidation of 1 to an unstable RhII,III derivative, and synthesis of other polytungstate analogs is possible The tetrabutylammonium salt of 1 exhibits modest catalytic reactivity for cyclopropanation

New Routes for Multiple Derivatization of Polyoxometalates. Bis(acetato)dirhodium-11-tungstophosphate, [(PO4)W11O35{Rh2(OAc)2}]5-

Rhodium−Carbon Bond Formation in Aqueous Solution. Synthesis, Structure, and Reactivity of the Functionalized Heteropolytungstates, [XW11O39RhCH2COOH]5,6- (X = P, Si)

The heteropolyanion [PW11O39RhCl]5- (1-Cl) was synthesized by hydrothermal reaction of [PW11O39]7- and RhCl3 at 150 °C for 20 h. The tetramethylammonium salt of 1-Cl was characterized by elemental analysis, 31P and 183W NMR, and solution molecular weight determination by ultracentrifugation (found 2744 ± 63, calcd 2816). The cyclic voltammogram of 1-Cl shows an irreversible reduction wave at −0.45 V vs Ag/AgCl, and controlled potential reduction at −0.5 V generates the dimeric metal−metal bonded species [(PW11O39Rh)2]10- (2). The composition and structure of 2 have been confirmed by elemental analysis of the cesium salt, analytical ultracentrifugation (ionic weight 5821 ± 186, calcd 5561), P and W NMR, and a limited structural analysis of the potassium salt, which revealed a Rh−Rh bond length of 2.52(2) A (K10[(PW11O39Rh)2]·xH2O, triclinic, P1; a = 12.703(6), b = 17.868(8), and c = 19.131(9) A; α = 96.56(2), β = 97.12(2), and γ = 91.318(33)°; Z = 2; V = 4278(3) A3). Aqueous solutions of 2 show an absorpt...

Rhodium Derivatives of Lacunary Heteropolytungstates Illustrate Metalloporphyrin Analogies. Reductive Dimerization to Rh2-Linked Keggin Moieties

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New Routes for Multiple Derivatization of Polyoxometalates. Bis(acetato)dirhodium-11-tungstophosphate, [(PO4)W11O35{Rh2(OAc)2}]5-

Rhodium−Carbon Bond Formation in Aqueous Solution. Synthesis, Structure, and Reactivity of the Functionalized Heteropolytungstates, [XW11O39RhCH2COOH]5,6- (X = P, Si)

Rhodium Derivatives of Lacunary Heteropolytungstates Illustrate Metalloporphyrin Analogies. Reductive Dimerization to Rh2-Linked Keggin Moieties