Polyoxometalate based open-frameworks (POM-OFs).

Polyoxometalate-based open frameworks (POM-OFs) are extended architectures incorporating metal-oxide cluster units and comprise an emergent family of materials with a large diversity of topologies, structural flexibility and functionality at the nanoscale. Not only do POM-OFs present a wide range of configurable structures, but also a have a vast array of physical properties which reflect the properties of the various 'modular' molecular inputs. Here we describe the methodologies that can be used to construct POM-OF materials with important catalytic, electronic, and structural properties and discuss the advantages compared to the metal organic framework analogues. We also show that it is possible to construct POM-OF materials and design and/or fine tune their functionality by manipulating the initially generated building block libraries as well as by controlling the self-assembly towards the specific intermediate (POM) species which is the chemical and structural "information" carrier of the targeted POM-OF material.

[1]  L. Cronin,et al.  Formation, self-assembly and transformation of a transient selenotungstate building block into clusters, chains and macrocycles. , 2014, Chemical communications.

[2]  Haiyan An,et al.  pH-controlled assembly of hybrid architectures based on Anderson-type polyoxometalates and silver coordination units. , 2014, Dalton transactions.

[3]  Asen Asenov,et al.  Towards polyoxometalate-cluster-based nano-electronics. , 2013, Chemistry.

[4]  L. Cronin,et al.  Polyoxometalate {W18O56XO6} clusters with embedded redox-active main-group templates as localized inner-cluster radicals. , 2013, Angewandte Chemie.

[5]  Xiang Wang,et al.  Assembly of multinuclear Ag complexes and Keggin polyoxometalates adjusted by organic ligands: syntheses, structures and luminescence , 2013 .

[6]  S. Ishikawa,et al.  Assembly of a Pentagonal Polyoxomolybdate Building Block, [Mo6O21]6–, into Crystalline MoV Oxides , 2013 .

[7]  M. Hashimoto,et al.  Dipotassium Diaquadiphosphatooctaperoxotetramolybdate, [K2(P2O7){MoO(O2)2}2{MoO(O2)2(OH2)}2]2– – a One‐Dimensional Double Chain Array of Polyanions Linked by Potassium Cations , 2013 .

[8]  Timothy R. Cook,et al.  Metal-organic frameworks and self-assembled supramolecular coordination complexes: comparing and contrasting the design, synthesis, and functionality of metal-organic materials. , 2013, Chemical reviews.

[9]  Leroy Cronin,et al.  A flow-system array for the discovery and scale up of inorganic clusters. , 2012, Nature chemistry.

[10]  A. Müller,et al.  From linking of metal-oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry. , 2012, Chemical Society reviews.

[11]  J. Poblet,et al.  Structure, properties and reactivity of polyoxometalates: a theoretical perspective. , 2012, Chemical Society reviews.

[12]  L. Cronin,et al.  Engineering polyoxometalates with emergent properties. , 2012, Chemical Society reviews.

[13]  N. Mizuno,et al.  Diamond-shaped [Ag4]4+ cluster encapsulated by silicotungstate ligands: synthesis and catalysis of hydrolytic oxidation of silanes. , 2012, Angewandte Chemie.

[14]  Leroy Cronin,et al.  Solution-phase monitoring of the structural evolution of a Molybdenum Blue nanoring. , 2012, Journal of the American Chemical Society.

[15]  N. Mizuno,et al.  Three-dimensional ordered arrays of 58×58×58 Å3 hollow frameworks in ionic crystals of M2Zn2-substituted polyoxometalates. , 2012, Angewandte Chemie.

[16]  Scott G. Mitchell,et al.  Exploring the rotational isomerism in non-classical Wells-Dawson anions {W18X}: a combined theoretical and mass spectrometry study. , 2012, Dalton transactions.

[17]  R. Cao,et al.  Photochromic hybrid materials of cucurbituril and polyoxometalates as photocatalysts under visible light. , 2012, Chemical communications.

[18]  N. Mizuno,et al.  Ionic crystals [M3O(OOCC6H5)6(H2O)3]4[α-SiW12O40] (M = Cr, Fe) as heterogeneous catalysts for pinacol rearrangement. , 2012, Inorganic chemistry.

[19]  Zhijuan Zhang,et al.  A multifunctional organic-inorganic hybrid structure based on Mn(III)-porphyrin and polyoxometalate as a highly effective dye scavenger and heterogenous catalyst. , 2012, Journal of the American Chemical Society.

[20]  Keigo Kamata,et al.  Catalytic oxidation of hydrocarbons with hydrogen peroxide by vanadium-based polyoxometalates , 2011 .

[21]  H. Furukawa,et al.  A multiunit catalyst with synergistic stability and reactivity: a polyoxometalate-metal organic framework for aerobic decontamination. , 2011, Journal of the American Chemical Society.

[22]  J. Marrot,et al.  Polyoxometalate-based metal organic frameworks (POMOFs): structural trends, energetics, and high electrocatalytic efficiency for hydrogen evolution reaction. , 2011, Journal of the American Chemical Society.

[23]  M. Speldrich,et al.  Molecular growth of a core-shell polyoxometalate. , 2011, Angewandte Chemie.

[24]  P. Gouzerh,et al.  Versatile host-guest chemistry and networking ability of the cyclic tungstophosphate {P8W48}: Two further manganese derivatives , 2011 .

[25]  L. Cronin,et al.  Controlling the Molecular Assembly of Polyoxometalates from the Nano to the Micron Scale: Molecules to Materials , 2011 .

[26]  Jie-ying Wu,et al.  Organic/polyoxometalate hybridization dyes: Crystal structure and enhanced two-photon absorption , 2011 .

[27]  Scott G. Mitchell,et al.  Extended polyoxometalate framework solids: two Mn(II)-linked {P8W48} network arrays. , 2011, Inorganic chemistry.

[28]  A. Bhaumik,et al.  Robust 1D open rack-like architecture in coordination polymers of Anderson POMs [{Na4(H2O)14}{Cu(gly)}2][TeMo6O24] and [{Cu(en)2}3{TeW6O24}]: synthesis, characterization and heterogeneous catalytic epoxidation of olefines. , 2010, Dalton transactions.

[29]  L. Cronin,et al.  Assembly of Pure Silver‐Tungsten‐Oxide Frameworks from Nanostructured Solution Processable Clusters and Their Evolution into Materials with a Metallic Component , 2010, Advanced materials.

[30]  L. Cronin,et al.  Cations in control: crystal engineering polyoxometalate clusters using cation directed self-assembly. , 2010, Dalton transactions.

[31]  Scott G. Mitchell,et al.  Modular inorganic polyoxometalate frameworks showing emergent properties: redox alloys. , 2010, Angewandte Chemie.

[32]  C. R. Mayer,et al.  Hybrid organic-inorganic polyoxometalate compounds: from structural diversity to applications. , 2010, Chemical reviews.

[33]  J. Marrot,et al.  Zeolitic polyoxometalates metal organic frameworks (Z-POMOF) with imidazole ligands and epsilon-Keggin ions as building blocks; computational evaluation of hypothetical polymorphs and a synthesis approach. , 2010, Physical chemistry chemical physics : PCCP.

[34]  N. Dalal,et al.  Cobalt, manganese, nickel, and vanadium derivatives of the cyclic 48-tungsto-8-phosphate [H(7)P(8)W(48)O(184)](33-). , 2010, Inorganic chemistry.

[35]  Qiushi Yin,et al.  A Fast Soluble Carbon-Free Molecular Water Oxidation Catalyst Based on Abundant Metals , 2010, Science.

[36]  Yang-guang Li,et al.  Two hexa-TM-containing (TM = Co2+ and Ni2+) {P2W12}-based trimeric tungstophosphates. , 2010, Dalton transactions.

[37]  Scott G. Mitchell,et al.  Face-directed self-assembly of an electronically active Archimedean polyoxometalate architecture. , 2010, Nature chemistry.

[38]  Yang-guang Li,et al.  Two New {P8W49} Wheel-shaped Tungstophosphates Decorated by Co(II), Ni(II) Ions , 2010 .

[39]  Leroy Cronin,et al.  Polyoxometalates: building blocks for functional nanoscale systems. , 2010, Angewandte Chemie.

[40]  L. Ye,et al.  Hydrothermal syntheses and characterizations of two novel frameworks constructed from polyoxometalates, metals and organic units. , 2010, Dalton transactions.

[41]  L. Cronin,et al.  Unveiling the Transient Template in the Self-Assembly of a Molecular Oxide Nanowheel , 2010, Science.

[42]  Guanggang Gao,et al.  The first ε-Keggin core of molybdogermanate in extended architectures of nickel(II) with N-donor ligands: syntheses, crystal structures and magnetic properties , 2009 .

[43]  N. Gadegaard,et al.  Supramolecular silver polyoxometalate architectures direct the growth of composite semiconducting nanostructures. , 2009, Angewandte Chemie.

[44]  Yang-guang Li,et al.  A new supramolecular assembly based on triple-Dawson-type polyoxometalate and 3d-4f heterometallic cluster. , 2009, Inorganic chemistry.

[45]  W. Wernsdorfer,et al.  Iron polyoxometalate single-molecule magnets. , 2009, Angewandte Chemie.

[46]  L. Cronin,et al.  Heteroatom-controlled kinetics of switchable polyoxometalate frameworks. , 2009, Journal of the American Chemical Society.

[47]  Yang-guang Li,et al.  An extended architecture built upon the double-Dawson-type polyoxoanion. , 2009, Dalton transactions.

[48]  L. Cronin,et al.  Controlling nucleation of the cyclic heteropolyanion {P8W48}: a cobalt-substituted phosphotungstate chain and network , 2009 .

[49]  L. Cronin,et al.  Probing the self-assembly of inorganic cluster architectures in solution with cryospray mass spectrometry: growth of polyoxomolybdate clusters and polymers mediated by silver(I) ions. , 2008, Journal of the American Chemical Society.

[50]  Leroy Cronin,et al.  Reversible redox reactions in an extended polyoxometalate framework solid. , 2008, Angewandte Chemie.

[51]  Yang-guang Li,et al.  Extended organic-inorganic hybrids based on Dawson and double-Dawson-type polyoxometalates. , 2008, Inorganic Chemistry.

[52]  L. Cronin,et al.  Polyoxometalate-mediated self-assembly of single-molecule magnets: {[XW9O34]2[Mn(III)4Mn(II)2O4(H2O)4]}12-. , 2008, Angewandte Chemie.

[53]  Shoutian Zheng,et al.  Designed synthesis of POM-organic frameworks from {Ni6PW9} building blocks under hydrothermal conditions. , 2008, Angewandte Chemie.

[54]  R. Thouvenot,et al.  Functionalization of polyoxometalates: towards advanced applications in catalysis and materials science. , 2008, Chemical communications.

[55]  L. Cronin,et al.  Molecular Growth of Polyoxometalate Architectures Based on [−Ag{Mo8}Ag−] Synthons: Toward Designed Cluster Assemblies , 2008 .

[56]  L. Cronin,et al.  Directing organic-inorganic hybrid molecular-assemblies of polyoxometalate crown-ether complexes with supramolecular cations , 2007 .

[57]  N. Mizuno,et al.  Design and syntheses of nano-structured ionic crystals with selective sorption properties , 2007 .

[58]  Jorge A. Fernández,et al.  Polyoxometalates with internal cavities: redox activity, basicity, and cation encapsulation in [Xn+P5W30O110](15-n)- Preyssler complexes, with X = Na+, Ca2+, Y3+, La3+, Ce3+, and Th4+. , 2007, Journal of the American Chemical Society.

[59]  N. Mizuno,et al.  Self-organization of all-inorganic dodecatungstophosphate nanocrystallites. , 2007, Journal of the American Chemical Society.

[60]  A. Bond,et al.  Structural, Electrochemical, and Spectroscopic Characterization of a Redox Pair of Sulfite-Based Polyoxotungstates: α-[W18O54(SO3)2]4- and α-[W18O54(SO3)2]5- , 2007 .

[61]  Y. Nodasaka,et al.  Crystalline Mo3VOx mixed-metal-oxide catalyst with trigonal symmetry. , 2007, Angewandte Chemie.

[62]  M. T. Pope,et al.  Tetrakis(dimethyltin)-containing tungstophosphate [{Sn(CH3)2}4(H2P4W24O92)2]28-: first evidence for a lacunary Preyssler ion. , 2006, Inorganic chemistry.

[63]  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.

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

[65]  J. Marrot,et al.  Hybrid 2D and 3D Frameworks Based on ϵ‐Keggin Polyoxometallates: Experiment and Simulation , 2005 .

[66]  N. Mizuno,et al.  Amphiphilic Guest Sorption of K2[Cr3O(OOCC2H5)6(H2O)3]2[α-SiW12O40] Ionic Crystal , 2005 .

[67]  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.

[68]  N. Mizuno,et al.  Structures and Sorption Properties of Ionic Crystals of Macrocation-Dawson-Type Polyoxometalates with Different Charges , 2005 .

[69]  L. Cronin,et al.  Controllable growth of chains and grids from polyoxomolybdate building blocks linked by silver(I) dimers. , 2005, Chemistry.

[70]  Canzhong Lu,et al.  A new polyoxomolybdate infinite chain complex containing β-[Mo8O26]4− linked up by two bonded Ag+ ions: {(Bu4N)2Ag2[Mo8O26]}n , 2004 .

[71]  Yan‐Qiong Sun,et al.  A novel organic-inorganic hybrid based on an 8-electron-reduced Keggin polymolybdate capped by tetrahedral, trigonal bipyramidal, and octahedral zinc: synthesis and crystal structure of (CH3NH3)(H2bipy)[Zn4(bipy)3(H2O)2MoV8MoVI4O36)(PO4)].4H2O. , 2004, Inorganic chemistry.

[72]  N. Mizuno,et al.  Zeotype ionic crystal of Cs5[Cr3O(OOCH)6(H2O)3][alpha-CoW12O40].7.5H2O with shape-selective adsorption of water. , 2004, Journal of the American Chemical Society.

[73]  G. Baronetti,et al.  The state of the art on Wells–Dawson heteropoly-compounds: A review of their properties and applications , 2003 .

[74]  Liying Duan,et al.  Synthesis, crystal structure, and photochromism of novel two-dimensional supramolecular networks based on Keggin-type polyoxoanion and lanthanide coordination cations. , 2003, Inorganic chemistry.

[75]  J. Marrot,et al.  Hybrid Organic–Inorganic 1D and 2D Frameworks with ε‐Keggin Polyoxomolybdates as Building Blocks , 2003 .

[76]  L. Lezama,et al.  A novel organic-inorganic hybrid based on a dinuclear copper complex supported on a keggin polyoxometalate. , 2003, Inorganic chemistry.

[77]  N. Mizuno,et al.  A Breathing Ionic Crystal Displaying Selective Binding of Small Alcohols and Nitriles: K3[Cr3O(OOCH)6(H2O)3][α‐SiW12O40]⋅16 H2O , 2002 .

[78]  Deqing Zhang,et al.  A novel two-dimensional mixed molybdenum–vanadium polyoxometalate with two types of cobalt(II) complex fragments as bridges , 2002 .

[79]  Jingping Wang,et al.  1D and 2D polyoxometalate-based composite compounds. Synthesis and crystal structure of [{Ba(DMSO)5(H2O)}2(SiMo12O40)] and [{Ba(DMSO)3(H2O)3}{Ba(DMSO)5(H2O)}(GeMo12O40)] , 2002 .

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

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

[82]  Valérie Cabuil,et al.  Designed Hybrid Organic−Inorganic Nanocomposites from Functional Nanobuilding Blocks , 2001 .

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

[84]  G. Desiraju The all-chemist. , 2000, Nature.

[85]  L. Cronin,et al.  Controlling Growth of Novel Solid-State Materials via Discrete Molybdenum-Oxide-Based Building Blocks as Synthons , 2000 .

[86]  M. I. Khan Novel Extended Solids Composed of Transition Metal Oxide Clusters , 2000 .

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

[88]  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 .

[89]  D. J. Chesnut,et al.  Organic/inorganic composite materials: the roles of organoamine ligands in the design of inorganic solids , 1999 .

[90]  R. Doedens,et al.  [M3 V18 O42 (H2 O)12 (XO4 )]⋅24 H2 O (M=Fe, Co; X=V, S): Metal Oxide Based Framework Materials Composed of Polyoxovanadate Clusters. , 1999, Angewandte Chemie.

[91]  P. Kögerler,et al.  Erratum to “From simple building blocks to structures with increasing size and complexity” , 1999 .

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

[93]  D. Katsoulis A Survey of Applications of Polyoxometalates. , 1998, Chemical reviews.

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

[95]  B. Krebs,et al.  Synthesis, structure of polymeric cobalt-containing heteropolytungstates and their applications in oxidation catalysis , 1997 .

[96]  R. Haushalter,et al.  New solids from old clusters: Syntheses and structures of [Cu(en)2]2[Mo8O26], [Cu(enMe)2]3[V15O36Cl] · 2.5H2O and Cs0.5[Ni(en)2]3[V18O42Cl] · 2en · 6H2O , 1997 .

[97]  R. Robson,et al.  An Infinite 2D Polyrotaxane Network in Ag2(bix)3(NO3)2 (bix = 1,4-Bis(imidazol-1-ylmethyl)benzene) , 1997 .

[98]  D. Proserpio,et al.  Polymeric Networks of Silver(I) and Copper(I) Ions Linked by an Anionic Acetonyl Derivative of Tetracyanoethylene , 1996 .

[99]  Lahcène Ouahab,et al.  Ein aus Keggin‐Einheiten aufgebautes, kettenartiges Heteropolyanion: Synthese und Struktur von (ET)8n[PMnW11O39]n · 2nH2O , 1995 .

[100]  M. Fujita,et al.  Interpenetrating Molecular Ladders and Bricks , 1995 .

[101]  F. Vögtle,et al.  Isomeric Lactam Catenanes and the Mechanism of their Formation , 1994 .

[102]  H. Sung,et al.  Polypyrrole doped with heteropolytungstate anions , 1994 .

[103]  J. Poblet,et al.  Relative basicities of the oxygen sites in [V10O28]6-. An analysis of the ab initio determined distributions of the electrostatic potential and of the Laplacian of charge density , 1992 .

[104]  A. Kjekshus,et al.  MULTICOMPONENT POLYANIONS PART 12, THE CRYSTAL STRUCTURE OF NA6MO18P2O62(H2O)24, A COMPOUND CONTAINING SODIUMCOORDINATED 18-MOLYBDODIPHOSPHATE ANIONS , 1975 .

[105]  C. K. Ingold The Nature of the Chemical Bond and the Structure of Molecules and Crystals , 1940, Nature.

[106]  A. Bond,et al.  Synthesis and redox properties of triarylmethane dye cation salts of anions [M6O19]2- (M = Mo, W). , 2011, Dalton transactions.

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

[108]  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.

[109]  Thomas J. Meyer,et al.  Comprehensive coordination chemistry II : from biology to nanotechnology , 2004 .

[110]  L. Ye,et al.  One- and two-dimensional framework materials constructed from the mixed Mo/V tetra-capped Keggin structure clusters and M(en)2 (M=Ni, Cu) complexes groups , 2001 .

[111]  A. Müller,et al.  [{MoVI8VIV4O36(VVO4)(VIVO)2}n]7n-: cappedα-Keggin fragments linked to a chain , 1997 .

[112]  Davide M. Proserpio,et al.  A three-dimensional ‘racemate’. Interpenetration of two enantiomeric networks of the SrSi2 topological type in the polymeric complex [Ag2(2,3-Me2pyz)3][SbF6]2(2,3-Me2pyz = 2,3-dimethylpyrazine) , 1996 .

[113]  Brendan F. Abrahams,et al.  A wellsian ‘three-dimensional’ racemate: eight interpenetrating, enantiomorphic (10,3)-a nets, four right- and four left-handed , 1996 .

[114]  M. Zaworotko,et al.  X-Ray crystal structure of C6H3(CO2H)3-1,3,5·1.5(4,4′-bipy): a ‘super trimesic acid’ chicken-wire grid , 1996 .

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

[116]  E. Coronado,et al.  [(Co(H2O)4)2(H2W12O42)]n6n-: A Novel Chainlike Heteropolyanion Formed by Paradodecatungstate and Cobalt(II) Ions , 1995 .

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

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

[119]  Robert K. Fitzgerel The Nature of the Chemical Bond and the Structure of Molecules and Crystals , 1941, Nature.