Functionalization of polyoxometalates: towards advanced applications in catalysis and materials science.

Functionalization via covalent grafting of organic functions allows to tune the redox and acid-base properties, and the solubility of polyoxometalates, to enhance their stability and biological activity and to reduce their toxicity, to facilitate their implementation in extended structures and functional devices. We discuss herein the electronic and binding connections, and the various synthesis methodologies. We emphasize on organonitrogen, organosilyl and organophosphonyl derivatives with special attention to synthesis, characterization and potential applications in catalysis and materials science. We also consider the giant molybdenum oxide-based clusters especially the porous capsule-type clusters (Keplerates) which have high relevance to this context.

[1]  A. Bakac,et al.  Unusually rapid homolysis of the cobalt-carbon bond in a macrocyclic benzylcobalt complex , 1987 .

[2]  M. Dressel,et al.  Extending the {(Mo)MO5}12M30 capsule keplerate sequence: a {Cr30} cluster of S=3/2 metal centers with a {Na(H2O)12} encapsulate. , 2007, Angewandte Chemie.

[3]  U. Kortz,et al.  The tungstogermanate [Ce20Ge10W100O376(OH)4(H2O)30]56-: a polyoxometalate containing 20 cerium(III) atoms. , 2007, Angewandte Chemie.

[4]  P. Kögerler,et al.  Pythagorean Harmony in the World of Metal Oxygen Clusters of the Mo 11 Type: Giant Wheels and Spheres both Based on a Pentagonal Type Unit , 2000 .

[5]  Tianbo Liu,et al.  Strong attraction among the fully hydrophilic {Mo72Fe30} macroanions. , 2005, Journal of the American Chemical Society.

[6]  B. Dawson The structure of the 9(18)-heteropoly anion in potassium 9(18)-tungstophosphate, K6(P2W18O62).14H2O , 1953 .

[7]  C. Hill,et al.  [{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20]36-: a molecular quantum spin icosidodecahedron. , 2005, Chemical communications.

[8]  Samar K. Das,et al.  Assembling nanosized ring-shaped synthons to an anionic layer structure based on the synergetically induced functional complementarity of their surface-sites: Na21[MoVI126MoV28O462H14(H2O)54(H2PO2)7]·xH2O (x ≈ 300) , 1999 .

[9]  Mingwen Wang,et al.  Synthesis and characterization of a new type of heteropolyanion: pentamolybdobis(n-propylarsonate), having two types of crystals under the same pH conditions in the same solution , 1988 .

[10]  P. Gouzerh,et al.  Merging organometallic chemistry with polyoxometalate chemistry , 2000, Chemistry.

[11]  H. Stoeckli-Evans,et al.  [(η6-p-PriC6H4Me)2Ru2Mo2O6(OMe)4]: a new tetranuclear mixed-metal oxo cluster presenting a cube-based chair structure , 1999 .

[12]  Haolong Li,et al.  Surfactant-Encapsulated Europium-Substituted Heteropolyoxotungstates: Structural Characterizations and Photophysical Properties , 2004 .

[13]  P. Delhaès,et al.  Toward New Organic/Inorganic Superlattices: Keggin Polyoxometalates in Langmuir and Langmuir−Blodgett Films , 1997 .

[14]  Qun Liu,et al.  Synthesis and characterization of organophosphorylpolyoxotungstate [α2-R2P2W17O61]6−(R=C6H11P(O), C6H5P(O), C6H11P(S), C6H5P(S)) , 2000 .

[15]  A. Müller,et al.  Reactions inside a porous nanocapsule/artificial cell: encapsulates' structuring directed by internal surface deprotonations. , 2006, Chemical communications.

[16]  T. Yamase,et al.  Photochemical formation of tire-shaped molybdenum blues: Topology of a defect anion, [Mo142O432H28(H2O)58]12- , 2002 .

[17]  P. Gouzerh,et al.  Main-Group Element, Organic, and Organometallic Derivatives of Polyoxometalates. , 1998, Chemical reviews.

[18]  H. Yashiro,et al.  Two-dimensional array of polyoxomolybdate nanoball constructed by Langmuir-Blodgett semiamphiphilic method , 2007 .

[19]  C. Hill,et al.  Stereoisomerism in polyoxometalates: structural and spectroscopic studies of bis(malate)-functionalized cluster systems. , 2005, Chemical Communications.

[20]  M. Antonietti,et al.  The interplay of colloidal organization and oxo-cluster chemistry: Polyoxometalate-silica hybrids - Materials with a nanochemical function. , 2000 .

[21]  Zhonghua Peng Rational synthesis of covalently bonded organic-inorganic hybrids. , 2004, Angewandte Chemie.

[22]  E. Wang,et al.  Theoretical study on the electronic spectrum and the origin of remarkably large third-order nonlinear optical properties of organoimide derivatives of hexamolybdates. , 2006, The journal of physical chemistry. B.

[23]  P. Gómez‐Romero Hybrid Organic–Inorganic Materials—In Search of Synergic Activity , 2001 .

[24]  D. Rehder,et al.  Artificial cells: temperature-dependent, reversible Li+-ion uptake/release equilibrium at metal oxide nanocontainer pores. , 2004, Angewandte Chemie.

[25]  S. Dong,et al.  Assembly of multilayer films containing iron(III)-substituted Dawson-type heteropolyanions and its electrocatalytic properties: cyclic voltammetry, electrochemical impedance spectroscopy and UV-Vis spectrometry , 2003 .

[26]  P. Gouzerh,et al.  Coordination chemistry of the hexavacant tungstophosphate [H2P2W12O48]12- with Fe(III) ions: towards original structures of increasing size and complexity. , 2005, Angewandte Chemie.

[27]  Soumyajit Roy,et al.  Urea as 'deus ex machina' in giant molybdenum blue type cluster synthesis: an unusual hybrid compound with perspectives for related nano, supramolecular and extended structures. , 2002, Chemical communications.

[28]  John E. Greedan,et al.  Geometrically frustrated magnetic materials , 2001 .

[29]  Enrico Drioli,et al.  Heterogeneous Photooxidation of Alcohols in Water by Photocatalytic Membranes Incorporating Decatungstate , 2003 .

[30]  J. Zubieta,et al.  Synthesis and characterization of oxomolybdate clusters containing coordinatively bound organo-diazenido units: the crystal and molecular structure of the hexanuclear diazenido-oxomolybdate, (NBun4)3[Mo6O18(N2C6H5)] , 1986 .

[31]  A. Müller,et al.  Soccer-playing metal oxide giant spheres: a first step towards patterning structurally well defined nano-object collectives. , 2002, Chemical communications.

[32]  Xiang-gao Meng,et al.  Two new bromo-functionalized organoimido derivatives of hexamolybdate: Synthesis, crystal structure, spectroscopic and electrochemical studies , 2007 .

[33]  H. Allcock,et al.  Structure of a new isopolymolybdate-cyclophosphazene complex , 1972 .

[34]  M. T. Pope,et al.  Heteropolyanions in non-polar solvents. Metalloporphyrin-like oxidation of chromium(III) to chromium(V) by iodosylbenzene , 1986 .

[35]  Shaoqin Liu,et al.  Functional Polyoxometalate Thin Films via Electrostatic Layer-by-Layer Self-Assembly , 2003 .

[36]  C. R. Mayer,et al.  Covalent Hybrid Materials Based on Nanolatex Particles and Dawson Polyoxometalates , 2005 .

[37]  A. Stein,et al.  Synthesis and characterization of 2D and 3D structures from organic derivatives of polyoxometalate clusters: role of organic moiety, counterion, and solvent. , 2001, Inorganic chemistry.

[38]  T. Yamase,et al.  Photochemical studies of alkylammonium molybdates. Part 12. O→Mo charge-transfer triplet-states-initiated self-assembly to {Mo154} ring- and tube-molybdenum-blues , 2003 .

[39]  J. Zubieta,et al.  Synthesis and structural investigation of polyoxomolybdate coordination compounds displaying a tetranuclear core. Crystal and molecular structures of [Bu4N]2[Mo4O10(OMe)2(OC6H4O)2] and to the diazenido complexes [Bu4N]2[Mo4O6(OMe)2(HNC6H4O)2(NNC6H5)4] and [Bu4N]2[Mo4O6(OMe)2(C10H6O2)2(NNC6H5)4]. Com , 1989 .

[40]  Z. Su,et al.  Density functional theory study on the first hyperpolarizabilities of organoimido derivatives of hexamolybdates. , 2005, The journal of physical chemistry. B.

[41]  J. Zubieta,et al.  Co-ordination complexes of polyoxomolybdates with a hexanuclear core: synthesis and structural characterization of (NBun4)2[Mo6O18(NNMePh)] , 1988 .

[42]  Jun Peng,et al.  Preparation and antibacterial activity of nanorod-amino acid polyoxometalates , 2007 .

[43]  C. Hill,et al.  Tetrairon and hexairon hydroxo/acetato clusters stabilized by multiple polyoxometalate scaffolds. Structures, magnetic properties, and chemistry of a dimer and a trimer. , 2007, Inorganic chemistry.

[44]  Hongbing Lu,et al.  Ultra-low-κ polyimide hybrid films via copolymerization of polyimide and polyoxometalates , 2007 .

[45]  J. Marrot,et al.  Effect of cyanato, azido, carboxylato, and carbonato ligands on the formation of cobalt(II) polyoxometalates: characterization, magnetic, and electrochemical studies of multinuclear cobalt clusters. , 2007, Chemistry.

[46]  Achim Müller,et al.  Polyoxometalate Chemistry: An Old Field with New Dimensions in Several Disciplines , 1991 .

[47]  Tianbo Liu An unusually slow self-assembly of inorganic ions in dilute aqueous solution. , 2003, Journal of the American Chemical Society.

[48]  G. Scorrano,et al.  Hybrid polyoxotungstates as second-generation POM-based catalysts for microwave-assisted H2O2 activation. , 2006, Organic letters.

[49]  J. Metzger,et al.  An unusual route to the isopolymolybdates; octamolybdate β-[Mo8O26]4− and hexamolybdate [Mo6O19]2−. Reaction of dioxomolybdenum complexes with triphenylphosphonium ylides. Crystal structures of the salts [PPh3CH2COOEt]2+[NH2Et]2+[Mo8O26]4−, [PPh3CH2COOEt]2+[Mo6O19]2−, and [PPh3CH2Ph]2+[Mo6O19]2− , 1985 .

[50]  Eugenio Coronado,et al.  Magnetic clusters from polyoxometalate complexes , 1999 .

[51]  Achim Müller,et al.  Polyoxometalates : from platonic solids to anti-retroviral activity , 1994 .

[52]  L. Ruhlmann,et al.  Naphthylimido-substituted hexamolybdate: preparation, crystal structures, solvent effects, and optical properties of three polymorphs. , 2007, Inorganic chemistry.

[53]  M. Axenovich,et al.  Exact ground state properties of the classical Heisenberg model for giant magnetic molecules , 2001 .

[54]  D. C. Duncan,et al.  Phenylimido Functionalization of alpha-[PW12O40]3-. , 2007, Inorganic chemistry.

[55]  C. Barnes,et al.  Functionalization of [MoW(5)O(19)](2-) with aromatic amines: synthesis of the first arylimido derivatives of mixed-metal polyoxometalates. , 2001, Inorganic chemistry.

[56]  B. Hasenknopf,et al.  Polyoxometalates: introduction to a class of inorganic compounds and their biomedical applications. , 2005, Frontiers in bioscience : a journal and virtual library.

[57]  C. Hill,et al.  Synthesis, structure, spectroscopic properties, and hydrolytic chemistry of organophosphonoyl polyoxotungstates of formula [C6H5P(O)]2Xn+W11O39(8-n)- (Xn+ = P5+, Si4+) , 1992 .

[58]  R. Thouvenot,et al.  Molybdenum oxo nitrosyl complexes. 2. Molybdenum-95 NMR studies of defect and complete Lindqvist-type derivatives. Crystal and molecular structure of (n-Bu4N)2[Mo6O17(OCH3)(NO)] , 1993 .

[59]  M. Lowe,et al.  Nuclear magnetic resonance studies of 4-hydroxypiperidinomethylphosphonic acid and its polyoxomolybdate conjugates , 1995 .

[60]  C. Hill,et al.  Poly(polyoxometalate) Dendrimers: Molecular Prototypes of New Catalytic Materials , 2000 .

[61]  D. Laurencin,et al.  Organometallic polyoxometalates: synthesis and structural analysis of (η6-arene) ruthenium-containing polyoxomolybdates , 2003 .

[62]  F. Caruso,et al.  Ultrathin Molybdenum Polyoxometalate−Polyelectrolyte Multilayer Films , 1998 .

[63]  Yunshan Zhou,et al.  Trapping cations in specific positions in tuneable "artificial cell" channels: new nanochemistry perspectives. , 2003, Angewandte Chemie.

[64]  T. Kunitake,et al.  Formation Process of Ultrathin Multilayer Films of Molybdenum Oxide by Alternate Adsorption of Octamolybdate and Linear Polycations , 1998 .

[65]  U. Kortz,et al.  A novel hexatungstate fragment stabilized by dimethyltin groups: [{(CH3)2Sn}2(W6O22)]4-. , 2006, Inorganic chemistry.

[66]  J. Zubieta,et al.  Chemistry of molybdenum and tungsten bis[hydrazido(2-1)] complexes. Preparations and x-ray crystal structures of [Mo(NNMePh)2(S2CNMe2)2], [Mo(NNPh2)2(S2CNMe2)2]Me2CO, [MoCl(NNMe2)2(PPh3)2]BPh4.CH2Cl2, and [Mo(NNMe2)2(bpy)2][BPh4]2.CH2Cl2 , 1982 .

[67]  C. R. Mayer,et al.  Organophosphoryl derivatives of trivacant tungstophosphates of general formula α-A-[PW9O34(RPO)2]5–: synthesis and structure determination by multinuclear magnetic resonance spectroscopy (31P, 183W)‡ , 1998 .

[68]  A. M. Khenkin,et al.  In vitro Antimyxovirus and Anti-Human Immunodeficiency Virus Activities of Polyoxometalates , 1995 .

[69]  P. Kögerler,et al.  Synergetic activation of "silent receptor" sites leading to a new type of inclusion complex: integration of a 64-membered ring comprising K+ and SO4(2-) ions into a molybdenum oxide-based nanoobject. , 2003, Chemical communications.

[70]  Tianbo Liu,et al.  Self-patterning of hydrophobic materials into highly ordered honeycomb nanostructures at the air/water interface. , 2007, Angewandte Chemie.

[71]  V. C. Gibson Dalton perspectives. Structural and bonding patterns in tetrahedral and pseudo-tetrahedral transition-metal complexes containing π-donor ligands , 1994 .

[72]  F. Hussain,et al.  The ball-shaped heteropolytungstates [{Sn(CH3)2(H2O)}24{Sn(CH3)2}12(A-XW9O34)12]36-. , 2005, Angewandte Chemie.

[73]  Triangular geometrical and magnetic motifs uniquely linked on a spherical capsule surface. , 2005, Angewandte Chemie.

[74]  J. Dilworth,et al.  The reactions of molybdenum oxo-complexes with substituted hydrazines. Part 5. The preparation of some organodiazenido-complexes of molybdenum , 1979 .

[75]  C. Hill,et al.  Sustained epoxidation of olefins by oxygen donors catalyzed by transition metal-substituted polyoxometalates, oxidatively resistant inorganic analogs of metalloporphyrins. , 1986, Journal of the American Chemical Society.

[76]  P. Gouzerh,et al.  Efficient preparation of functionalized hybrid organic/inorganic Wells-Dawson-type polyoxotungstates. , 2005, Journal of the American Chemical Society.

[77]  Zhonghua Peng,et al.  An efficient and convenient reaction protocol to organoimido derivatives of polyoxometalates. , 2001, Journal of the American Chemical Society.

[78]  W. Xin,et al.  Synthesis and characterization of the second example of a new type of heteropolyanion: pentamolybdobis(allylarsonate) , 1989 .

[79]  P. Gouzerh,et al.  Developing Remote Metal Binding Sites in Heteropolymolybdates , 2003 .

[80]  Dirk Volkmer,et al.  Polyoxometalate-based electro- and photochromic dual-mode devices. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[81]  W. Clegg,et al.  Novel Conjunction of Hetero(macro)cycles and a Pentamolybdodiphosphonate Cage , 1994 .

[82]  T. Aida,et al.  A molybdenum crown cluster forms discrete inorganic-organic nanocomposites with metalloporphyrins. , 2004, Angewandte Chemie.

[83]  A. Dolbecq,et al.  Functionalization of polyoxometalates by carboxylato and azido ligands: macromolecular complexes and extended compounds. , 2006, Chemical communications.

[84]  Soumyajit Roy,et al.  Linking Giant Molybdenum Oxide Based Nano-Objects Based on Well-Defined Surfaces in Different Phases , 2005 .

[85]  Jun Wang,et al.  Study on highly ordered luminescent Langmuir–Blodgett films of heteropolytungstate complexes containing lanthanide , 2002 .

[86]  Ivan V. Kozhevnikov,et al.  Catalysis by Heteropoly Acids and Multicomponent Polyoxometalates in Liquid-Phase Reactions. , 1998, Chemical reviews.

[87]  A. Rheingold,et al.  A polyoxometalate incorporating an organoimido ligand: preparation and structure of [Mo5O18(MoNC6H4CH3)]2- , 1992 .

[88]  B. J. Melde,et al.  Direct Synthesis of Ordered Macroporous Silica Materials Functionalized with Polyoxometalate Clusters , 2001 .

[89]  F. Hussain,et al.  The Hybrid Organic‐Inorganic 2‐D Material (CsNa2[{Sn(CH3)2}3(H2O)4(β‐XW9O33)]·7H2O)∞ (X = AsIII, SbIII) and Its Solution Properties , 2004 .

[90]  R. Neumann,et al.  Organometallic[bond]polyoxometalate hybrid compounds: metallosalen compounds modified by Keggin type polyoxometalates. , 2003, Inorganic chemistry.

[91]  J. Enemark,et al.  Principles of structure, bonding, and reactivity for metal nitrosyl complexes , 1974 .

[92]  E. Wang,et al.  Fabrication and characterization of heteropolyanion Langmuir–Blodgett films , 1999 .

[93]  P. Judeinstein Synthesis and properties of polyoxometalates based inorganic-organic polymers , 1992 .

[94]  R. Thouvenot,et al.  Functionalized heteropolyanions: high-valent metal nitrido fragments incorporated into a Keggin polyoxometalate structure. , 2002, Chemical communications.

[95]  A. Müller,et al.  An Unusual Polyoxomolybdate: Giant Wheels Linked to Chains , 1997 .

[96]  W. You,et al.  Synthesis and characterization of organophosphoryl polyoxotungstates [RP(O)]2Xn+W11O39(8−n)− (Xn+ = P5+, Si4+, Ge4+, Ga3+) , 2003 .

[97]  Samar K. Das,et al.  Cross-linking nanostructured spherical capsules as building units by crystal engineering: related chemistry , 2000 .

[98]  Lixin Wu,et al.  Surfactant-Encapsulated Europium-Substituted Heteropolyoxotungatate: The Structural Characterization and Photophysical Properties of Its Solid State, Solvent-Casting Film, and Langmuir−Blodgett Film , 2003 .

[99]  U. Kortz,et al.  Heteropolymolybdates of phosphate, phosphonate, and phosphite functionalized by glycine. , 2003, Inorganic chemistry.

[100]  T. Yamase,et al.  Photoreductive self-assembly from [Mo7O24]6- to carboxylates-coordinated {Mo142} Mo-blue nanoring in the presence of carboxylic acids. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[101]  J. Tabet,et al.  Investigation of the reactivity of arylamines, organo-hydrazines and tolylisocyanate towards [PW12-xMxO40]n- Keggin anions. , 2005, Dalton transactions.

[102]  T. Yamase,et al.  Photo- and Electrochromism of Polyoxometalates and Related Materials. , 1998, Chemical reviews.

[103]  D. Sutton Co-ordination chemistry of aryldiazonium cations: aryldiazenato (arylazo) complexes of transition metals, and the aryldiazenato–nitrosyl analogy , 1975 .

[104]  A. Müller,et al.  Soluble molybdenum blues-"des Pudels Kern". , 2000, Accounts of chemical research.

[105]  E. Coronado,et al.  A new BEDT-TTF salt and polypyrrole films containing the chiral polyoxometalate [H 4Co 2Mo 10O 38] 6 , 2005 .

[106]  D. Volkmer,et al.  Biologically inspired polyoxometalate-surfactant composite materials. Investigations on the structures of discrete, surfactant-encapsulated clusters, monolayers, and Langmuir- Blodgett films of (DODA)(40)(NH4)(2)[(H2O)(n)subset of Mo132O372(CH3CO2)(30)(H2O)(72)]. , 2000 .

[107]  U. Kortz,et al.  13-tungstoborate stabilized by an organostannoxane hexamer. , 2007, Inorganic chemistry.

[108]  R. Thouvenot,et al.  analysis, UV-visible, electrochemical and multinuclear NMR characterization , 1999 .

[109]  Samar K. Das,et al.  Giant Ring-Shaped Building Blocks Linked to Form a Layered Cluster Network with Nanosized Channels: [Mo124VIMo28VO429(μ3-O)28H14(H2O)66.5]16− , 1999 .

[110]  R. Neumann,et al.  Phenanthroline-polyoxometalate hybrid compounds and the observation of intramolecular charge transfer. , 2005, Inorganic chemistry.

[111]  D. Volkmer,et al.  Structure and properties of the dendron-encapsulated polyoxometalate (C52H60NO12)12[(Mn(H2O))3(SbW9O33)2], a first generation dendrizyme , 2002 .

[112]  C. R. Mayer,et al.  Bis- and Tetrakis(organosilyl) Decatungstosilicate, [γ-SiW10O36(RSi)2O]4− and [γ-SiW10O36(RSiO)4]4−: Synthesis and Structural Determination by Multinuclear NMR Spectroscopy and Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry , 2000 .

[113]  J. Nelson,et al.  Charge-transfer hybrids containing covalently bonded polyoxometalates and ferrocenyl units. , 2004, Inorganic chemistry.

[114]  P. Gouzerh,et al.  Two Novel Polyoxomolybdates Containing the (MoNO)3⊕ Unit: [Mo5Na(NO)O13(OCH3)4]2⊖ and [Mo6(NO)O18]3⊖ , 1989 .

[115]  H. Stoeckli-Evans,et al.  [(p-PriC6H4Me)4 Ru4Mo4O16]: an amphiphilic organoruthenium oxomolybdenum cluster presenting a unique framework geometry , 1997 .

[116]  J. Keggin,et al.  Structure of the Molecule of i2-Phosphotungstic , 1933, Nature.

[117]  M. T. Pope,et al.  Self‐Assembly of Supramolecular Polyoxometalates: The Compact, Water‐Soluble Heteropolytungstate Anion [As 12IIICe 16III(H2O)36W148O524]76− , 1997 .

[118]  R. Strandberg,et al.  The structure of tetraguanidinium pentamolybdodiphenylphosphonate , 1988 .

[119]  R. Kim,et al.  Direct evidence on the existence of [Mo132]Keplerate-type species in aqueous solution. , 2007, Inorganic chemistry.

[120]  I. Kozhevnikov Catalysis by polyoxometalates , 2002 .

[121]  R. Neumann,et al.  Molecular oxygen and oxidation catalysis by phosphovanadomolybdates. , 2006, Chemical communications.

[122]  P. Kögerler,et al.  Classical and quantum magnetism in giant Keplerate magnetic molecules. , 2001, Chemphyschem : a European journal of chemical physics and physical chemistry.

[123]  H. T. Evans THE CRYSTAL STRUCTURES OF AMMONIUM AND POTASSIUM MOLYBDOTELLURATES , 1948 .

[124]  Hang Sun,et al.  Onionlike hybrid assemblies based on surfactant-encapsulated polyoxometalates. , 2007, Angewandte Chemie.

[125]  Xiaodong Zhai,et al.  Fabrication and photoluminescence of hybrid organized molecular films of a series of gemini amphiphiles and europium(III)-containing polyoxometalate. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[126]  Ji Young Kim,et al.  1H NMR study of pyridine-type ligands coordinated to the paramagnetic polyoxometalates, [CoIIW11MO39]n− (M=CoII, NiII, CuII, or FeIII) , 2001 .

[127]  A. Stein,et al.  Design and analysis of chain and network structures from organic derivatives of polyoxometalate clusters. , 2002, Inorganic chemistry.

[128]  R. Schinazi,et al.  Polyoxometalates in Medicine. , 1998, Chemical reviews.

[129]  J. Zubieta,et al.  Synthesis and chemical characterization of diazenido derivatives of oxomolybdate clusters: The structures of the tetranuclear complexes [Mo4O8)(OR)2(NNC6H5]2- (R = CH3 OR C2H5) , 1986 .

[130]  Tianbo Liu,et al.  A complete macroion-"blackberry" assembly-macroion transition with continuously adjustable assembly sizes in {Mo132} water/acetone systems. , 2007, Journal of the American Chemical Society.

[131]  Soumyajit Roy,et al.  Changeable pore sizes allowing effective and specific recognition by a molybdenum-oxide based "Nanosponge": en route to sphere-surface and nanoporous-cluster chemistry. , 2002, Angewandte Chemie.

[132]  E. Coronado,et al.  Polyoxometalate monolayers in Langmuir-Blodgett films. , 2005, Chemistry.

[133]  E. Wang,et al.  Preparation and nonlinear optical properties of ultrathin composite films containing both a polyoxometalate anion and a binuclear phthalocyanine , 2002 .

[134]  P. Kögerler,et al.  Competing spin phases in geometrically frustrated magnetic molecules. , 2004, Physical review letters.

[135]  I. Moriguchi,et al.  Characterization and Electrochromic Properties of Ultrathin Films Self-Assembled from Poly(diallyldimethylammonium) Chloride and Sodium Decatungstate , 1998 .

[136]  A. Müller,et al.  Molecular growth from a Mo176 to a Mo248 cluster , 1999, Nature.

[137]  R. Errington,et al.  Covalent immobilization of a TiW5 polyoxometalate on derivatized silicon surfaces. , 2005, Angewandte Chemie.

[138]  A. Beatty,et al.  Organoimido-polyoxometalates as polymer pendants , 2000 .

[139]  Shaoqin Liu,et al.  A Thin-Film Electrochromic Device Based on a Polyoxometalate Cluster , 2002 .

[140]  Achim Müller,et al.  The Beauty of Symmetry , 2003, Science.

[141]  T. Yamase,et al.  Ferromagnetic Exchange Interactions for Cu612+ and Mn612+ Hexagons Sandwiched by Two B-α-[XW9O33]9- (X = AsIII and SbIII) Ligands in D3d-Symmetric Polyoxotungstates , 2006 .

[142]  M. Malacria,et al.  A general strategy for ligation of organic and biological molecules to Dawson and Keggin polyoxotungstates. , 2007, Organic letters.

[143]  Fang‐Chung Chen,et al.  Synthesis of main-chain polyoxometalate-containing hybrid polymers and their applications in photovoltaic cells , 2005 .

[144]  M. Cloninger,et al.  Synthesis of carbohydrate‐linked poly(polyoxometalate) poly(amido)amine dendrimers , 2005 .

[145]  Shaoqin Liu,et al.  From molecular modules to modular materials , 2004 .

[146]  C. Marquer,et al.  Polyoxomolybdates functionalized with phosphonocarboxylates. , 2003, Inorganic chemistry.

[147]  P. Kögerler,et al.  Building blocks as disposition in solution: [{MoVIO3(H2O)}10{VIVO(H2O)}20{(MoVI/MoVI5O21)(H2O)3}10({MoVIO2(H2O)2}5/2)2 ({NaSO4}5)2]20–, a giant spherical cluster with unusual structural features of interest for supramolecula , 1999 .

[148]  John Emsley,et al.  Nature's building blocks : an A-Z guide to the elements , 2001 .

[149]  C. Hamaker,et al.  Functionalization of heteropolyanions-osmium and rhenium nitrido derivatives of Keggin- and Dawson-type polyoxotungstates: synthesis, characterization and multinuclear ((183)W, (15)N) NMR, EPR, IR, and UV/Vis fingerprints. , 2006, Chemistry.

[150]  R. Thouvenot,et al.  Sensing the chirality of Dawson lanthanide polyoxometalates [alpha1-LnP2W17O61]7- by multinuclear NMR spectroscopy. , 2008, Chemistry.

[151]  A. Dress,et al.  Self-assembly in aqueous solution of wheel-shaped Mo154 oxide clusters into vesicles , 2003, Nature.

[152]  C. Sanchez,et al.  DESIGN OF HYBRID ORGANIC-INORGANIC MATERIALS SYNTHESIZED VIA SOL-GEL CHEMISTRY , 1994 .

[153]  R. Thouvenot,et al.  Coordination Chemistry of Polyoxometalates: Rational Synthesis of the Mixed Organosilyl Derivatives of Trivacant Polyoxotungstates α‐A‐[PW9O34(tBuSiO)3 (RSi)]3− and α‐B‐[AsW9O33(tBuSiO)3(HSi)]3− , 1996 .

[154]  Eugenio Coronado,et al.  Polycxometalates: From Magnetic Clusters to Molecular Materials , 1995 .

[155]  M. T. Pope,et al.  New polyoxometalate/starch nanomaterial: synthesis, characterization and antitumoral activity , 2003 .

[156]  P. Kögerler,et al.  A variety of combinatorially linkable units as disposition:† from a giant icosahedral Keplerate to multi-functional metal–oxide based network structures , 1999 .

[157]  P. Gouzerh,et al.  Anderson‐Type Heteropolymolybdates Containing Tris(alkoxo) Ligands: Synthesis and Structural Characterization , 2002 .

[158]  A. Beatty,et al.  A p-cyanophenylimido hexamolybdate: preparation and structure of [(n-C4H9)4N]2[Mo6O18(N-p-C6H4CN)] † , 2005 .

[159]  R. Thouvenot,et al.  Lindqvist‐Type (Aryldiazenido)polyoxomolybdates − Synthesis, and Structural and Spectroscopic Characterization of Compounds of the Type (nBu4N)3[Mo6O18(N2Ar)] , 2003 .

[160]  R. Thouvenot,et al.  A NEW CLASS OF ORGANOSILYL DERIVATIVES OF POLYOXOANIONS : ATTACHMENT OF ALKYL- AND ARYSYLYL GROUPS ON TRIVACANT TUNGSTOSILICATE , 1991 .

[161]  V. Young,et al.  A Diazoalkane Derivative of a Polyoxometalate: Preparation and Structure of [Mo6 O18 (NNC(C6 H4 OCH3 )CH3 )](2-). , 1999, Angewandte Chemie.

[162]  Achim Müller,et al.  Inorganic chemistry goes protein size: a Mo368 nano-hedgehog initiating nanochemistry by symmetry breaking. , 2002, Angewandte Chemie.

[163]  Dante Gatteschi,et al.  Polyoxometalates: Very Large Clusters-Nanoscale Magnets. , 1998, Chemical reviews.

[164]  R. Thouvenot,et al.  New Hybrid Covalent Networks Based on Polyoxometalates: Part 1. Hybrid Networks Based on Poly(ethyl methacrylate) Chains Covalently Cross-linked by Heteropolyanions: Synthesis and Swelling Properties , 2000 .

[165]  T. Mitra,et al.  Mimicking biological cation-transport based on sphere-surface supramolecular chemistry: simultaneous interaction of porous capsules with molecular plugs and passing cations. , 2007, Chemistry.

[166]  J. Tabet,et al.  Functionalization of polyoxometalates: from Lindqvist to Keggin derivatives. 1. synthesis, solution studies, and spectroscopic and ESI mass spectrometry characterization of the rhenium phenylimido tungstophosphate [PW11O39(ReNC6H5)]4-. , 2004, Inorganic chemistry.

[167]  P. Gouzerh,et al.  Assembly of a polyoxometalate into an anisotropic gel. , 2003, Chemical communications.

[168]  A. Müller,et al.  Hierarchic patterning: architectures beyond 'giant molecular wheels'. , 2001, Chemical communications.

[169]  R. Ostrander,et al.  Ensheathing a Polyoxometalate: Convenient Systematic Introduction of Organoimido Ligands at Terminal Oxo Sites in [Mo6O19]2- , 1994 .

[170]  A. Neels,et al.  Amphiphilic organorutheniumoxomolybdenumoxovanadium clusters , 1998 .

[171]  C. R. Mayer,et al.  A nanoscale hybrid system based on gold nanoparticles and heteropolyanions. , 2002, Angewandte Chemie.

[172]  Müller,et al.  Thirty Electrons "Trapped" in a Spherical Matrix: A Molybdenum Oxide-Based Nanostructured Keplerate Reduced by 36 Electrons. , 2000, Angewandte Chemie.

[173]  M. Chaplin,et al.  Self‐Association Based on Interfacial Structured Water Leads to {Mo154}≈1165 Super Clusters: A Dielectric Study , 2007 .

[174]  Lixin Wu,et al.  Thermotropic mesomorphic behavior of surfactant-encapsulated polyoxometalate hybrids. , 2006, The journal of physical chemistry. B.

[175]  F. Hussain,et al.  Polyoxoanions functionalized by diorganotin groups: the tetrameric, chiral tungstoarsenate(III), [{Sn(CH3)2(H2O)}2{Sn(CH3)2}As3(alpha-AsW9O33)4]21-. , 2005, Chemical communications.

[176]  W. You,et al.  Synthesis, spectroscopic properties and crystal structure of organophosphoryl polyoxotungstate α-[Bu4N]3H[PhCH2P(O)]2SiW11O39 , 2006 .

[177]  From simple building blocks to structures with increasing size and complexity , 1999 .

[178]  Jun Wang,et al.  Langmuir-Blodgett films based on europium-substituted heteropolytungstate and their luminescence properties , 2003 .

[179]  D. Laurencin,et al.  Framework fluxionality of organometallic oxides: synthesis, crystal structure, EXAFS, and DFT studies on [[Ru(eta6-arene)]4Mo4O16] complexes. , 2004, Chemistry.

[180]  Jinhua Chen,et al.  Organometallic oxides: oxidation of [(.eta.-C5Me5)Mo(CO)2]2 with O2 to form syn-[(.eta.-C5Me5)MoCl]2(.mu.-Cl)2(.mu.-O), syn-[(.eta.-C5Me5)MoCl]2(.mu.-Cl)(.mu.-CO3H)(.mu.-O), and [C5Me5O][(.eta.-C5Me5)Mo6O18] , 1992 .

[181]  J. Zubieta,et al.  Synthesis and characterization of oxomolybdate clusters containing co-ordinatively bound diazenido units. The crystal and molecular structure of the octanuclear oxomolybdate (NHEt3)2(NBu4)2[Mo8O20(NNPh)6] , 1985 .

[182]  Lifeng Fu,et al.  Effective energy transfer and luminescence of LB films based on europium-substituted heteropolytungstate , 2002 .

[183]  R. Thouvenot,et al.  Synthesis, characterization and study of the chromogenic properties of the hybrid polyoxometalates [PW11O39(SiR)2O]3− (R = Et, (CH2)nCHCH2 (n = 0, 1, 4), CH2CH2SiEt3, CH2CH2SiMe2Ph)☆ , 2007 .

[184]  E. Radkov,et al.  A comprehensive series of Group 14 derivatives of the plenary mixed-metal polyoxometalate [PNbW11O40]4− , 2000 .

[185]  L. Baker,et al.  New fundamental type of inorganic complex: hybrid between heteropoly and conventional coordination complexes. Possibilities for geometrical isomerisms in 11-, 12-, 17-, and 18-heteropoly derivatives , 1970 .

[186]  Gaoyang Xie,et al.  X-ray crystal structure of guanidinium hexamolybdobis(o-nitrophenylarsonate)monohydrate, (CN3)H6)5[(o-NO2C6H4As)2Mo6 O25H]·H2O , 1990 .

[187]  C. Qin,et al.  A linear bifunctionalized organoimido derivative of hexamolybdate: Convenient synthesis and crystal structure , 2005 .

[188]  D. Powell,et al.  Towards main-chain-polyoxometalate-containing hybrid polymers: a highly efficient approach to bifunctionalized organoimido derivatives of hexamolybdates. , 2002, Angewandte Chemie.

[189]  Leroy Cronin,et al.  Polyoxometalate clusters, nanostructures and materials: from self assembly to designer materials and devices. , 2007, Chemical Society reviews.

[190]  M. T. Pope,et al.  Stable Organic Derivatives of Heteropoly Anions, Pentamolybdobisphosphonates. , 1975 .

[191]  Yongge Wei,et al.  Organic‐Inorganic Hybrids: Preparation and Structural Characterization of (Bu4N)2[Mo6O17(NAr)2] and (Bu4N)2[Mo6O18(NAr)] (Ar = o‐CH3C6H4) , 2005 .

[192]  R. Neumann,et al.  The high-valent iron-oxo species of polyoxometalate, if it can be made, will be a highly potent catalyst for C-H hydroxylation and double-bond epoxidation. , 2005, Journal of the American Chemical Society.

[193]  D. Volkmer,et al.  Ultrathin composite films incorporating the nanoporous isopolyoxomolybdate "Keplerate" (NH4)(42)[Mo132O372(CH3COO)(30)(H2O)(72)]. , 2000 .

[194]  U. Kortz,et al.  The wheel-shaped Cu20 tungstophosphate [Cu20Cl(OH)24(H2O)12(P8W48O184)]25- ion. , 2005, Angewandte Chemie.

[195]  K. Wieghardt,et al.  Reductive Nitrosylation of V2O5 and MoO3 with Hydroxylamine in the Presence of 1,4,7-Triazacyclononane , 2001 .

[196]  A. Müller,et al.  Chameleon water: assemblies confined in nanocapsules , 2005 .

[197]  V. Day,et al.  Synthesis, characterization, and interconversion of the niobotungstic acid Nb2W4O19H3- and its anhydride and alkyl/silyl esters , 1987 .

[198]  P. Gouzerh,et al.  Coordination chemistry of the hexavacant tungstophosphate [H2P(2W12O48]12-: synthesis and characterization of iron(III) complexes derived from the unprecedented {P2W14O54} fragment. , 2005, Chemical communications.

[199]  S. Shaik,et al.  What is the difference between the manganese porphyrin and corrole analogues of cytochrome P450's compound I? , 2001, Chemistry.

[200]  A. Rheingold,et al.  Polyoxometalate clusters as building blocks: preparation and structure of bis(hexamolybdate) complexes covalently bridged by organodiimido ligands , 1995 .

[201]  Hang Sun,et al.  Polyoxometalate-based vesicle and its honeycomb architectures on solid surfaces. , 2005, Journal of the American Chemical Society.

[202]  R. Neumann,et al.  Synthesis, characterization and catalytic activity of a Wilkinson's type metal-organic-polyoxometalate hybrid compound. , 2003, Chemical communications.

[203]  M. Antonietti,et al.  Highly photoluminescent polyoxometaloeuropate-surfactant complexes by ionic self-assembly. , 2005, Chemistry.

[204]  R. Thouvenot,et al.  Synthesis and Characterization of New Organosilyl Derivatives of Polyoxometalates (nBu4N)2[NbW5O19SiRR′2] (R = R′ = Et, iPr, OtBu, Ph;R = tBu and R′ = Me) – X‐ray Crystal Structure of (nBu4N)2[NbW5O19SiPh3] , 2007 .

[205]  M. T. Pope,et al.  Chelated heteroatoms in polyoxometalates and the topological equivalence of [CoIII(en)] to type II cis-dioxometal centers. Synthesis and structure of [[Co(en)(mu-OH)2Co(en)}[PW10O37Co(en)]2]8- and [K subset[Co(en)WO4][WO(H2O)](PW9O34)2]12-. , 2005, Chemical communications.

[206]  J. Cox,et al.  Modification of electrodes with nanostructured films containing dirhodium-substituted polyoxometalates , 2004 .

[207]  N. Gadegaard,et al.  From polyoxometalate building blocks to polymers and materials: the silver connection , 2007 .

[208]  D. Volkmer,et al.  Surfactant-encapsulated clusters (SECs): (DODA)20(NH4)[H3Mo57V6(NO)6O183(H2O)18], a case study. , 2000, Chemistry.

[209]  R. Neumann,et al.  New heterogeneous polyoxometalate based mesoporous catalysts for hydrogen peroxide mediated oxidation reactions. , 2004, Journal of the American Chemical Society.

[210]  Enrico Drioli,et al.  Heterogenization of polyoxometalates on the surface of plasma-modified polymeric membranes , 2006 .

[211]  C. Hill,et al.  Enantiomerically pure polytungstates: chirality transfer through zirconium coordination centers to nanosized inorganic clusters. , 2005, Angewandte Chemie.

[212]  D. Powell,et al.  Polyoxometalates covalently bonded with terpyridine ligands. , 2003, Chemical communications.

[213]  E. Wang,et al.  Why Does Disubstituted Hexamolybdate with Arylimido Prefer to Form an Orthogonal Derivative? Analysis of Stability, Bonding Character, and Electronic Properties on Molybdate Derivatives by Density Functional Theory (DFT) Study , 2004 .

[214]  V. Young,et al.  A Functionalized Polyoxometalate Bearing a Ferrocenylimido Ligand: Preparation and Structure of [(FcN)Mo6O18]2− , 1995 .

[215]  E. Steckhan,et al.  Electrochemical Properties of Polyoxometalates as Electrocatalysts. , 1998, Chemical reviews.

[216]  Enrico Drioli,et al.  Solvent-free, heterogeneous photooxygenation of hydrocarbons by hyflon membranes embedding a fluorous-tagged decatungstate. , 2006, Chemical communications.

[217]  Soumyajit Roy,et al.  Multifunctional metal oxide based nanoobjects: spherical porous capsules/artificial cells and wheel-shaped species with unprecedented materials properties , 2005 .

[218]  C. Hill Progress and challenges in polyoxometalate-based catalysis and catalytic materials chemistry , 2007 .

[219]  K. Nomiya,et al.  Syntheses, Characterization, and X-ray Crystal Structures of Mono-Lacunary Dawson Polyoxometalate-Based Organosilyl Complexes , 2006 .

[220]  M. Antonietti,et al.  Colloidal organization and clusters: self-assembly of polyoxometalate-surfactant complexes towards three-dimensional organized structures. , 2001, Chemphyschem : a European journal of chemical physics and physical chemistry.

[221]  Zhonghua Peng,et al.  Synthesis and Optical Properties of Conjugated Polymers Containing Polyoxometalate Clusters as Side-Chain Pendants , 2005 .

[222]  C. R. Mayer,et al.  Organic-Inorganic Hybrids Based on Polyoxometalates. 5.(1) Synthesis and Structural Characterization of Bis(organophosphoryl)decatungstosilicates [gamma-SiW(10)O(36)((RPO)(2)](4)(-). , 1999, Inorganic chemistry.

[223]  C. R. Mayer,et al.  New organosilyl derivatives of the Dawson polyoxometalate [alpha2-P2W17O61(RSi)2O]6-: synthesis and mass spectrometric investigation. , 2004, Chemistry.

[224]  Tianbo Liu,et al.  Deprotonations and charges of well-defined {Mo72Fe30} nanoacids simply stepwise tuned by pH allow control/variation of related self-assembly processes. , 2006, Journal of the American Chemical Society.

[225]  Martin Dressel,et al.  En route to coordination chemistry under confined conditions in a porous capsule: Pr3+ with different coordination shells. , 2004, Chemical communications.

[226]  E. Coronado,et al.  Recent advances in polyoxometalate-containing molecular conductors , 2005 .

[227]  Changwen Hu,et al.  Polyoxometalates nanoparticles: synthesis, characterization and carbon nanotube modification , 2004 .

[228]  C. R. Mayer,et al.  Hybrid Hydrogels Obtained by the Copolymerization of Acrylamide with Aggregates of Methacryloyl Derivatives of Polyoxotungstates. A Comparison with Polyacrylamide Hydrogels with Trapped Aggregates , 2000 .

[229]  J. Stalick,et al.  Two heteropoly anions containing organic groups. Crystal and molecular structures of ammonium pentamolybdobis(methylphosphonate) pentahydrate, (NH4)4[(CH3P)2Mo5O21].cntdot.5H2O, and sodium tetramethylammonium pentamolybdobis(ethylammoniumphosphonate) pentahydrate, Na[N(CH3)4][(NH3C2H4P)2Mo5O21].cntd , 1976 .

[230]  D. Crommelin,et al.  Abstracts of papers , 2005, Pharmaceutisch Weekblad.

[231]  Shaoqin Liu,et al.  Smart polyoxometalate-based nitrogen monoxide sensors. , 2004, Analytical chemistry.

[232]  Bailin Chen,et al.  Monitoring the growth of polyoxomolybdate nanoparticles in suspension by flow field-flow fractionation. , 2005, Journal of the American Chemical Society.

[233]  P. Franzon,et al.  Controlled modulation of conductance in silicon devices by molecular monolayers. , 2006, Journal of the American Chemical Society.

[234]  Shiwei Zhang,et al.  Self-assembly of a novel nanoscale giant cluster: [Mo176O496(OH)32(H2O)80]† , 1998 .

[235]  A. Rheingold,et al.  A superoctahedral complex derived from a polyoxometalate: thehexakis(arylimido)hexamolybdate anion[Mo6(NAr)6O13H]- , 1997 .

[236]  W. Casey,et al.  Rates of ligand exchange between >FeIII-OH2 functional groups on a nanometer-sized aqueous cluster and bulk solution. , 2007, Inorganic chemistry.

[237]  Haolong Li,et al.  A surfactant-encapsulated polyoxometalate complex towards a thermotropic liquid crystal. , 2005, Chemical communications.

[238]  J. Zubieta,et al.  Coordination complexes of polyoxomolybdate anions. Characterization of a tetranuclear core from reactions in methanol: syntheses and structures of two polyoxomolybdate alcoholates, (MePPh3)2[Mo4O10(OCH3)6] and (n-Bu4N)2[Mo4O10(OCH3)2(OC6H4O)2], and their relationship to a general class of tetranucle , 1987 .

[239]  E. Coronado,et al.  Hybrid Organic/Inorganic Langmuir–Blodgett Films. A Supramolecular Approach to Ultrathin Magnetic Films , 1999 .

[240]  L. Long,et al.  A keplerate magnetic cluster featuring an icosidodecahedron of Ni(II) ions encapsulating a dodecahedron of La(III) ions. , 2007, Journal of the American Chemical Society.

[241]  Jingping Wang,et al.  Organosilyl derivatives of trivacant tungstophosphate of general formula α-A-[PW9O34(RSiO)3(RSi)]3−: Synthesis and structure determination by X-ray crystallography , 2003 .

[242]  J. Zubieta,et al.  Tungsten-organoimido chemistry. The crystal and molecular structures of [(n-C4H9)4N][W(NC6H4CH3)Cl5] and [(n-C4H9)4N][C7H7NH3][W2OCl8(NC6H4CH3)2] , 1992 .

[243]  S. McGrath,et al.  Mono- and di-functional aromatic amines with p-alkoxy substituents as novel arylimido ligands for the hexamolybdate ion , 2003 .

[244]  Hui Zhang,et al.  Luminescent logic function of a surfactant-encapsulated polyoxometalate complex. , 2006, Chemical communications.

[245]  Shaoqin Liu,et al.  The structure of self-assembled multilayers with polyoxometalate nanoclusters. , 2002, Journal of the American Chemical Society.

[246]  Z.-P. Liu Chemical reactions at surfaces and interfaces from first principles: Theory and application , 2004 .

[247]  Kazuko Matsumoto The crystal structure of guanidinium hexamolybdobis(phenylarsonate) tetrahydrate, (CN3H6)4[C6H5As)2Mo6O25H2] 4H2O. , 1978 .

[248]  D. Powell,et al.  Molecular and polymeric hybrids based on covalently linked polyoxometalates and transition-metal complexes. , 2005, Angewandte Chemie.

[249]  P. Kögerler,et al.  A potassium selective 'nanosponge' with well defined pores. , 2002, Chemical communications.

[250]  Zhonghua Peng,et al.  Hybrid Molecular Materials Based on Covalently Linked Inorganic Polyoxometalates and Organic Conjugated Systems. , 2001, Angewandte Chemie.

[251]  D. Rehder,et al.  Countercation transport modeled by porous spherical molybdenum oxide based nanocapsules. , 2006, Chemistry, an Asian journal.

[252]  H. Yashiro,et al.  Regular two-dimensional molecular array of photoluminescent Anderson-type polyoxometalate constructed by Langmuir-Blodgett technique. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[253]  Y. Wang,et al.  An Easy Route to Monofunctionalized Organoimido Derivatives of the Lindqvist Hexamolybdate , 2004 .

[254]  R. Thouvenot,et al.  Organic-inorganic hybrids based on polyoxometalates. 6. Syntheses, structure, and reactivity of the bis(tert-butylsilyl)decatungstophosphate [(gamma-PW10O36)(t-BuSiOH)2]3-. , 2000, Inorganic chemistry.

[255]  R. Thouvenot,et al.  Phenylimido derivatives of [Mo6O19]2−: syntheses, X-ray structures, vibrational, electrochemical, 95Mo and 14N NMR studies , 1994 .

[256]  Qun Liu,et al.  Synthesis and spectroscopic characterization of organophosphoryl polyoxotungstates [C6H11P(O)]2Xn+W11O39(8−n)− (Xn+=P5+, Si4+, B3+, Ga3+) , 2000 .

[257]  R. Schinazi,et al.  Synthesis, characterization, and anti-human immunodeficiency virus activity of water-soluble salts of polyoxotungstate anions with covalently attached organic groups. , 1992, Journal of medicinal chemistry.

[258]  Samar K. Das,et al.  Linking Icosahedral, Strong Molecular Magnets {Mo} to Layers—A Solid‐State Reaction at Room Temperature , 2000 .

[259]  P. Judeinstein Polyoxometallates based macromolecules , 1994 .

[260]  Mayer,et al.  Incorporation of Magnetic Nanoparticles in New Hybrid Networks Based on Heteropolyanions and Polyacrylamide. , 1999, Angewandte Chemie.

[261]  Polymerizable inorganic–organic hybrid: Syntheses and structures of mono-lacunary Dawson polyoxometalate-based olefin-containing organosilyl derivatives , 2007 .

[262]  R. Thouvenot,et al.  Organic‐Inorganic Hybrids based on Polyoxometalates. Part 8 Synthesis and Spectroscopic Characterization of the Heterosilylated Anions [PW9O34(tBuSiO)3(SiR)]3‐ (R = ‐CH3, ‐CH=CH2, ‐CH2‐CH=CH2, ‐(CH2)4‐CH=CH2) ‐ X‐ray Crystal Structure of [nBu4N]3[PW9O34(tBuSiO)3(SiCH2‐CH=CH2)] , 2004 .

[263]  R. Neumann,et al.  Strategies for oxidation catalyzed by polyoxometalates at the interface of homogeneous and heterogeneous catalysis , 2005 .

[264]  D. Powell,et al.  Hybrid molecular dumbbells: bridging polyoxometalate clusters with an organic pi-conjugated rod. , 2002, Angewandte Chemie.

[265]  Y. Wang,et al.  Synthesis, structure and supramolecular assembly in the crystalline state of a bifunctionalized arylimido derivative of hexamolybdate , 2004 .

[266]  A. Bagno,et al.  Photooxidation in Water by New Hybrid Molecular Photocatalysts Integrating an Organic Sensitizer with a Polyoxometalate Core , 2004 .

[267]  J. Cox,et al.  Nanocomposite Multilayer Film of a Ruthenium Metallodendrimer and a Dawson-Type Polyoxometalate as a Bifunctional Electrocatalyst , 2002 .

[268]  E. Coronado,et al.  Application of the Langmuir–Blodgett Technique to Polyoxometalates: Towards New Magnetic Films , 1997 .

[269]  G. Tourné,et al.  Ligand- and Metal-Exchange Reactions on Substituted Lacunary Heteropolytungstates , 1983 .

[270]  M. T. Pope,et al.  Chiral polyoxotungstates. 1. Stereoselective interaction of amino acids with enantiomers of [Ce(III)(alpha1-P2W17O61)(H2O)x]7-. The structure of DL-[Ce2(H2O)8(P2W17O61)2]14-. , 2001, Inorganic chemistry.

[271]  R. Neumann,et al.  Computer-generated high-valent iron--oxo and manganese--oxo species with polyoxometalate ligands: how do they compare with the iron--oxo active species of heme enzymes? , 2004, Angewandte Chemie.

[272]  E. Coronado,et al.  Magnetic molecular conductors. , 2004, Chemical reviews.

[273]  R. Errington,et al.  Functionalisation of [Mo6O19]2– with aromatic amines: synthesis and structure of a hexamolybdate building block with linear difunctionality , 1995 .

[274]  Eugenio Coronado,et al.  Polyoxometalate-Based Molecular Materials. , 1998, Chemical reviews.

[275]  E. Coronado,et al.  Hybrid molecular conductors , 2005 .

[276]  Tianbo Liu,et al.  Thermodynamic properties of the unique self-assembly of {Mo72Fe30} inorganic macro-ions in salt-free and salt-containing aqueous solutions. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[277]  I. Weinstock Homogeneous-Phase Electron-Transfer Reactions of Polyoxometalates. , 1998, Chemical reviews.

[278]  I. Weinstock,et al.  Complex catalysts from self-repairing ensembles to highly reactive air-based oxidation systems , 2007 .

[279]  R. Thouvenot,et al.  Synthesis and characterization of Keggin derivatives containing an [Mo(NO)]3+ unit: (n-Bu4N)4[PM11O39{Mo(NO)}] (M Mo, W) , 1994 .

[280]  Shaoqin Liu,et al.  Polyoxometalates as pH-sensitive probes in self-assembled multilayers. , 2002, Chemical communications.

[281]  Tianbo Liu Supramolecular structures of polyoxomolybdate-based giant molecules in aqueous solution. , 2002, Journal of the American Chemical Society.

[282]  R. Thouvenot,et al.  A New Class of Functionalized Polyoxometalates: Synthetic, Structural, Spectroscopic, and Electrochemical Studies of Organoimido Derivatives of [Mo6O19]2- , 2000 .

[283]  R. Neumann,et al.  Characterization of manganese(V)-oxo polyoxometalate intermediates and their properties in oxygen-transfer reactions. , 2006, Journal of the American Chemical Society.

[284]  M. T. Pope Heteropoly and isopoly anions as oxo complexes and their reducibility to mixed-valence blues , 1972 .

[285]  J. Zubieta,et al.  Derivatized polyoxomolybdates. Synthesis and characterization of oxomolybdate clusters containing coordinatively bound diazenido units. Crystal and molecular structure of the octanuclear oxomolybdate (NHEt3)2(n-Bu4N)2[Mo8O20(NNPh)6] and comparison to the structures of the parent oxomolybdate .alpha. , 1987 .

[286]  V. Artero,et al.  Reduction of the Phosphododecamolybdate Ion by Phosphonium Ylides and Phosphanes , 2000 .

[287]  J. Silverton,et al.  A new structural type for heteropoly anions. The crystal structure of (NH4)2H6(CeMo12O42).12H2O , 1968 .

[288]  M. T. Pope,et al.  Polyoxometalate Derivatives with Multiple Organic Groups. 1. Synthesis and Structures of Tris(organotin) .beta.-Keggin and .alpha.-Dawson Tungstophosphates , 1994 .

[289]  C. R. Mayer,et al.  Hybrid Cyclic Dimers of Divacant Heteropolyanions: Synthesis, Mass Spectrometry (MALDI‐TOF and ESI‐MS) and NMR Multinuclear Characterisation , 2004 .

[290]  R. Thouvenot,et al.  Synthesis and characterization of the Keggin-type ruthenium-nitrido derivative [PW11O39{RuN}]4- and evidence of its electrophilic reactivity. , 2007, Journal of the American Chemical Society.

[291]  Jingping Wang,et al.  An organosilyl derivative of trivacant tungstophosphate. Synthesis, characterization and crystal structure determination of α-A-[NBun4]3 [PW9O34(C2H5SiO)3(C2H5Si)] , 2003 .

[292]  C. Hill,et al.  Redox‐Active Coordination Polymers from Esterified Hexavanadate Units and Divalent Metal Cations , 2006 .

[293]  R. Schinazi,et al.  Relationship of the Molecular Size and Charge Density of Polyoxometalates to Their anti-gp120-CD4-binding Activity , 1994 .

[294]  C. Dekock,et al.  Synthesis and molecular structure of di-and tetra-nuclear nitrido(oxo)molybdenum(VI) compounds containing trimethylsiloxy and n-base ligands , 1989 .

[295]  Y. Wang,et al.  A kinetically controlled trans bifunctionalized organoimido derivative of the Lindqvist-type hexamolybdate: synthesis, spectroscopic characterization, and crystal structure of (n-Bu4N)2{trans-[Mo6O17(NAr)2]} (Ar = 2,6-dimethylphenyl). , 2005, Inorganic chemistry.

[296]  J. Zubieta,et al.  Synthesis and characterization of a tetranuclear oxomolybdate containing coordinatively bound diazenido units. [Mo4O8(OCH3)2(NNC6H5)4]2−: a versatile precursor for the synthesis of complexes with the [Mo(NNC6H5)2]2+ unit , 1985 .

[297]  W. Knoth Derivatives of heteropolyanions. 1. Organic derivatives of W12SiO404-, W12PO403-, and Mo12SiO404- , 1979 .

[298]  D. Rehder,et al.  Porous inorganic capsules in action: modelling transmembrane cation-transport parameter-dependence based on water as vehicle. , 2005, Chemical communications.

[299]  Müller,et al.  Archimedean Synthesis and Magic Numbers: "Sizing" Giant Molybdenum-Oxide-Based Molecular Spheres of the Keplerate Type. , 1999, Angewandte Chemie.

[300]  M. Wark,et al.  Functionalized mesoporous silica films as a matrix for anchoring electrochemically active guests. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[301]  C. R. Mayer,et al.  Aminobenzylphosphonate functionalized polyoxometalates , 2004 .

[302]  A. Dress,et al.  Giant metal-oxide-based spheres and their topology: from pentagonal building blocks to keplerates and unusual spin systems , 2001 .

[303]  Kinetic precipitation of solution-phase polyoxomolybdate followed by transmission electron microscopy: a window to solution-phase nanostructure. , 2004, Chemistry.

[304]  P. Judeinstein,et al.  Synthesis and multispectroscopic characterization of organically modified polyoxometalates , 1991 .

[305]  T. Yamase Anti-tumor, -viral, and -bacterial activities of polyoxometalates for realizing an inorganic drug , 2005 .

[306]  U. Kortz,et al.  Heteropolymolybdates of AsIII, SbIII, BiIII, SeIV, and TeIV functionalized by amino acids. , 2002, Angewandte Chemie.

[307]  J. Zubieta,et al.  Oxovanadium and Oxomolybdenum Clusters and Solids Incorporating Oxygen‐Donor Ligands , 2007 .

[308]  Glenn Westwood,et al.  Traps for cations , 2003, Nature materials.

[309]  Zhonghua Peng,et al.  Enantiopure 1,1'-binaphthyl-based polyoxometalate-containing molecular hybrids. , 2005, Inorganic chemistry.

[310]  J. Saillard,et al.  Bonding analysis of transition metal NNR end-on complexes and comparison with isoelectronic NNR2 species , 2001 .

[311]  M. T. Pope,et al.  Organotin and organogermanium linkers for simple, direct functionalization of polyoxotungstates. , 2004, Dalton transactions.

[312]  Jing Liu,et al.  Organophosphoryl polyoxotungstates α-[R2PW9O34]5− [R = PhP(S), C6H11P(O), H2NCH(n-Pr)P(O)] , 2000 .

[313]  Roald Hoffmann,et al.  Building Bridges Between Inorganic and Organic Chemistry (Nobel Lecture) , 1982 .

[314]  M. T. Pope,et al.  New liposome-encapsulated-polyoxometalates: synthesis and antitumoral activity. , 2005, Journal of inorganic biochemistry.

[315]  Samar K. Das,et al.  On the option of generating novel type surfaces with multiphilic ligands within the cavity of a giant metal–oxide based wheel type cluster: chemical reactions with well-defined nanoobjects , 2001 .

[316]  H. Allcock,et al.  Crystal and molecular structure of a new hexamolybdate-cyclophosphazene complex , 1973 .

[317]  P. Richard,et al.  Synthesis and structure of a new organometallic polyoxomolybdate , 2004 .

[318]  E. Wang,et al.  Synthesis and characterization of polyoxometalate nanowires based on a novel microemulsion process , 2003 .

[319]  F. Emmerling,et al.  Chitosan-encapsulated Keggin Anion [Ti2W10PO40]7−. Synthesis, Characterization and Cellular Uptake Studies , 2006 .

[320]  Eric J. Hayden,et al.  Creating monolayers and thin films of a novel bis(alkyl) substituted asymmetrical polyoxotungstate, [[CH3(CH2)11Si]2OSiW11O39]4- using the Langmuir-Blodgett technique. , 2003, Chemical communications.

[321]  D. Volkmer,et al.  Toward nanodevices: Synthesis and characterization of the nanoporous surfactant-encapsulated keplerate (DODA)(40)(NH4)(2)[(H2O)(n)subset of Mo132O372(CH3COO)(30)(H2O)(72)]. , 2000 .

[322]  F. Hussain,et al.  Trimeric, Cyclic Dimethyltin-Containing Tungstophosphate [{(Sn(CH3)2)(Sn(CH3)2O)(A-PW9O34)}3]21− , 2007 .

[323]  A. Rheingold,et al.  An Organoimido Derivative of the Hexatungstate Cluster: Preparation and Structure of [W6O18(NAr)]2- (Ar = 2,6-(i-Pr)2C6H3) , 1995 .

[324]  J. S. Anderson,et al.  Constitution of the Poly-acids , 1937, Nature.