Polyoxometalate Chemistry PDF
Preview Polyoxometalate Chemistry
ADVISORY BOARD L. H. Gade D. Darensbourg UniversitätHeidelberg TexasA&MUniversity Germany CollegeStation,Texas,USA M. L. H. Green H. B. Gray UniversityofOxford CaliforniaInstituteofTechnology Oxford,UnitedKingdom Pasadena,California,USA A. E. Merbach P. A. Lay LaboratoiredeChimieetBioanorganiqueEFPL, UniversityofSydney Lausanne,Switzerland Sydney,Australia P. J. Sadler J. Reedijk UniversityofWarwick LeidenUniversity Warwick,England Leiden,TheNetherlands K. Wieghardt Y. Sasaki Max-Planck-Institut HokkaidoUniversity Mülheim,Germany Sapporo,Japan AcademicPressisanimprintofElsevier 50HampshireStreet,5thFloor,Cambridge,MA02139,UnitedStates 525BStreet,Suite1800,SanDiego,CA92101-4495,UnitedStates TheBoulevard,LangfordLane,Kidlington,Oxford,OX51GB,UnitedKingdom 125LondonWall,London,EC2Y5AS,UnitedKingdom Firstedition2017 Copyright©2017,ElsevierInc.Allrightsreserved Nopartofthispublicationmaybereproducedortransmittedinanyformorbyanymeans, electronicormechanical,includingphotocopying,recording,oranyinformationstorageand retrievalsystem,withoutpermissioninwritingfromthepublisher.Detailsonhowtoseek permission,furtherinformationaboutthePublisher’spermissionspoliciesandour arrangementswithorganizationssuchastheCopyrightClearanceCenterandtheCopyright LicensingAgency,canbefoundatourwebsite:www.elsevier.com/permissions. Thisbookandtheindividualcontributionscontainedinitareprotectedundercopyrightby thePublisher(otherthanasmaybenotedherein). 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ISBN:978-0-12-811105-5 ISSN:0898-8838 ForinformationonallAcademicPresspublications visitourwebsiteathttps://www.elsevier.com/books-and-journals Publisher:ZoeKruze AcquisitionEditor:PoppyGarraway EditorialProjectManager:ShellieBryant ProductionProjectManager:VigneshTamil CoverDesigner:GregHarris TypesetbySPiGlobal,India CONTRIBUTORS J.J.Baldov´ı InstitutodeCienciaMolecular(ICMol),UniversidaddeValencia,Paterna,Spain J.J.Carbo´ UniversitatRoviraiVirgili,Tarragona,Spain S.Cardona-Serra InstitutodeCienciaMolecular(ICMol),UniversidaddeValencia,Paterna,Spain W.H.Casey UniversityofCalifornia,Davis,CA,UnitedStates E.Coronado InstitutodeCienciaMolecular(ICMol),UniversidaddeValencia,Paterna,Spain L.Cronin WestCHEM,SchoolofChemistry,TheUniversityofGlasgow,Glasgow,UnitedKingdom S.A.Eghtesadi TheUniversityofAkron,Akron,OH,UnitedStates R.J.Errington SchoolofChemistry,NewcastleUniversity,NewcastleuponTyne,UnitedKingdom A.Gaita-Arin˜o InstitutodeCienciaMolecular(ICMol),UniversidaddeValencia,Paterna,Spain J.R.Gala´n-Mascaro´s InstituteofChemicalResearchofCatalonia(ICIQ),Tarragona;ICREA,PasseigLlu´ıs Companys,Barcelona,Spain Y.Gao TheUniversityofAkron,Akron,OH,UnitedStates Y.V.Geletii EmoryUniversity,Atlanta,GA,UnitedStates S.Goberna-Ferro´n InstituteofChemicalResearchofCatalonia(ICIQ),Tarragona,Spain C.L.Hill EmoryUniversity,Atlanta,GA,UnitedStates J.Hu StateKeyLaboratoryofChemicalResourceEngineering,BeijingUniversityofChemical Technology,Beijing,PRChina P.Ko€gerler InstituteofInorganicChemistry,RWTHAachenUniversity,Aachen;PeterGru€nberg Institute(PGI-6),ResearchCentreJu€lich,Ju€lich,Germany ix x Contributors S.M.Lauinger EmoryUniversity,Atlanta,GA,UnitedStates C.-G.Lin StateKeyLaboratoryofChemicalResourceEngineering,BeijingUniversityofChemical Technology,Beijing,PRChina T.Liu TheUniversityofAkron,Akron,OH,UnitedStates D.-L.Long WestCHEM,SchoolofChemistry,TheUniversityofGlasgow,Glasgow,UnitedKingdom H.N.Miras WestCHEM,SchoolofChemistry,TheUniversityofGlasgow,Glasgow,UnitedKingdom K.Y.Monakhov InstituteofInorganicChemistry,RWTHAachenUniversity,Aachen;PeterGru€nberg Institute(PGI-6),ResearchCentreJu€lich,Ju€lich,Germany M.Moors PeterGru€nbergInstitute(PGI-7),ResearchCentreJu€lich,Ju€lich,Germany R.Neumann WeizmannInstituteofScience,Rehovot,Israel J.M.Poblet UniversitatRoviraiVirgili,Tarragona,Spain Y.-F.Song StateKeyLaboratoryofChemicalResourceEngineering,BeijingUniversityofChemical Technology,Beijing,PRChina J.Soriano-Lo´pez InstituteofChemicalResearchofCatalonia(ICIQ);UniversitatRoviraiVirgili,Tarragona, Spain Q.Yin EmoryUniversity,Atlanta,GA,UnitedStates PREFACE Volume 69 of Advances in Inorganic Chemistry explores the latest trends and research results in the versatile and expanding area of Polyoxometalate Chemistry. Polyoxometalates are not only an extraordinary class of inor- ganicmoleculeswithavastrangeofstructures,theyhaveaseeminglynever ending set of possible applications and yet still challenge our fundamental ideas of structure and bonding in inorganic chemistry. Their extraordinary potential today is matched by their history, and the growth of poly- oxometalate cluster science has been made possible by advances in crystal- lography, mass spectroscopy, and NMR. InChapter1,Croninandcoworkersgiveanoverviewofthestateofthe art in understanding the assembly of polyoxometalate clusters. Given that polyoxometalateclustersspanalargerangeofmetalionnuclearityandsize, understanding the mechanismof assembly is a really bigchallenge. Indeed, howdolocalstructureandbondingrulestranslatebeyondafewatomstothe hundredsofheavyatomsfoundinamolybdenumclusterring?Insighttothis process is given along with an overview of how dynamic assembly and the self-organization of clusters across length scales is now being investigated. InChapter2,thethemeofassemblyiscontinuedbeyondthesupermolecule by Liu whereby the formation of polyoxometalate blackberries, i.e., super macroion interactions, is explored. This contribution shows how poly- oxometalate colloids with extraordinary properties and functions can be fashioned and also demonstrates that there are new guiding principles responsible for the structuring of gigantic macroanions. In Chapter 3, Neumann explores electron transfer reactions of metal oxide clusters and showshowmoleculardesigncanleadtoreactivitycontrolandsmall-molecule activation.Thedesignofmetaloxidecatalystsandphoto-andelectrosystems is a very important emerging area in this context. In Chapter 4, Casey summarizesrecentworkexploringoxygen–isotopeexchangeandmetastable dissociation in oxides. The kinetics here provides a great insight into how metal oxides can form clusters across the periodic table not only Mo, W, butalsoofNb.InChapter5,Hillandcoworkersconcentrateontheexplo- sion of work exploring polyoxometalate-based water oxidation catalysts (WOCs) and describe the synthesis, structure, and kinetic properties of a rangeofextremelygoodWOCsandalsoexplaintheprospectsthatunder- standing WOC might beimportant in the development of earth-abundant xi xii Preface developmentofpolyoxometalatesasactivecomponentsinsolar-fuelproduc- tion. This theme is continued in Chapter 6 by Poblet and coworkers who describethedetailedbehaviorofaspecificPOM-cobaltoxideWOCsystem. In Chapter 7, Song andcolleagues broaden the catalyst for energy theme to energy storage and sensors describing how POMs are being used as active components in electrode materials for batteries and electrochemical sensors. In Chapter 8, Coronado and coworkers outline an ambitious plan for the useofmagneticpolyoxometalateclustersasspinqubits.Drivenbythediscov- eryofPOM-basedsingleionmagnets,thisislikelytobecomeamajorareaof electronicnanotechnology,andChapter9byKo€gerlerandcoworkersexpand thistobothspintronicsandsingle-moleculeelectronicsexplaininghownew types of switching behavior could lead to fundamentally new types of com- puting systems. Finally in Chapter 10, Errington describes the fascinating developments in nonaqueous polyoxometalate synthesis and shows that hydrolysis, protonation, and reduction can be explored in organic solvents. Here,againPOMshavesomethinguniquetoofferbothintermsofstructure, mechanism, and reactivity. We Editors are very excited by this collection of important research chapters and are grateful to the authors for their effort in producing such engaging,exciting,andcutting-edgechapters.Thissurelywillbeanimpor- tant resource for the expanding number of researchers tempted to explore the riches of polyoxometalate cluster science. R. VAN ELDIK Editor of Advances in Inorganic Chemistry Emeritus Professor of Inorganic Chemistry, University of Erlangen–Nuremberg, Germany Professor of Inorganic Chemistry, Jagiellonian University, Krakow, Poland L. CRONIN Co-Editor of this volume Regius Professor of Chemistry, University of Glasgow, United Kingdom December 2016 CHAPTER ONE Exploring Self-Assembly and the Self-Organization of Nanoscale Inorganic Polyoxometalate Clusters H.N. Miras, D.-L. Long, L. Cronin1 WestCHEM,SchoolofChemistry,TheUniversityofGlasgow,Glasgow,UnitedKingdom 1Correspondingauthor:e-mailaddress:[email protected] Contents 1. IntroductiontoPolyoxometalateChemistry 2 1.1 Background 2 1.2 ClassificationofthePolyoxometalateFamily 2 2. FromSerendipitytoDirectedAssembly 4 3. SyntheticMethodologies 6 3.1 LigandsandMetalCationsasAssemblyDirectingMotifs 6 3.2 TemplatedAssembly 10 3.3 ReductivelyTriggeredAssembly 17 4. POM-BasedSupramolecularStructures 18 4.1 POMNanostructures 18 5. FromSelf-AssembledtoSelf-OrganizingClusterSystems 21 6. Conclusions 24 References 25 Abstract Polyoxometalates (POMs) are a family of self-assembled molecular clusters with an unmatchedrangeofphysicalproperties,structuralfeatures,andsizes.Thedevelopment ofappropriatesyntheticmethodologies,analyticaltechniques,andapproacheswhich allowtheconstructiveexplorationofthevastparameterspaceofPOMchemistryiscru- cialfortheunderstandingandcontroloftheunderlyingcomplexreactionsmaskedby theself-assembly.Thischapterdiscussesthemainaspectsoftheself-assemblythatgov- ernthePOM-basedchemicalsystemsandthemethodologiesusedforthegeneration oflibrariesofmolecularsynthonsthatcanbeusedfortheconstructionoflargemolec- ularmoieties.Wewillillustratehowtheeffectivecombinationofsyntheticapproaches inthisareacontributedtoourdeeperunderstandingoftheself-assemblybyrevealing important mechanistic information. The final sections are devoted to discussing the self-organizationofthepreassembledmolecularcomponentsintocomplexfunctional macrostructures. AdvancesinInorganicChemistry,Volume69 #2017ElsevierInc. 1 ISSN0898-8838 Allrightsreserved. http://dx.doi.org/10.1016/bs.adioch.2016.12.001 2 H.N.Mirasetal. 1. INTRODUCTION TO POLYOXOMETALATE CHEMISTRY 1.1 Background Polyoxoanionsorpolyoxometalates(POMs)(1)areadiverseclassofanionic metal-oxoclustersconstructedmainlybyearlytransitionmetals(V,Nb,Ta, Mo,W)inhighoxidationstates.Almosttwocenturieshavepassedsincethe discovery of the first POM species by Berzelius in 1826 (2), and this was followed by the first detailed crystallographic characterization by Keggin (3). POMscontinue to attractthe attentionof research groupsdue to their remarkable molecular and electronic structural diversity, unexpected func- tionalities, and their application in diverse scientific fields, e.g., catalysis, medicine, and materials science (4–6). More specifically, in the last two decades(7,8),adramaticincreaseinthenumberofstructurallycharacterized POM compounds due to developments in instrumentation and novel syntheticapproacheshasoccurred.Thishasbeendrivenbythedevelopment offastandroutinesinglecrystaldatacollectionoflargeandcomplexPOM architectures in combination with advances in spectroscopic techniques such as electrospray-ionization mass spectrometry and heteronuclear NMR. As such these studies have allowed researchers to bridge the gap betweensolutionandsolidstateofself-assembledchemicalsystemsandgain insight into mechanistic aspects of the complex underlying chemical occurrences(9,10).Additionally,researchhasalsoexploredthesupramolec- ular aspects of polyoxometalate chemistry, i.e., the organization of small fragments to larger species via weak interactions (11). This idea has been drivenbythethesisthateventhemolecularclusterscanbetreatedashaving a set of transferable building blocks that can be reliably utilized in the formationofnewgiganticstructures,materials,andfunctionalsupramolec- ularformations,triggeredtherapiddevelopmentofsyntheticapproachesin an effort to better understand the parameters that affect and control the self-assembly-governed processes. 1.2 Classification of the Polyoxometalate Family There is a vast number of anionic multinuclear species which fall into the polyoxometalatecategoryandexhibitaplethoraofstructuralfeatures,com- positions,andsizesrangingfrom1to5.6nm(12).Thus,theirorganization inaninformativemannerintermsofeithertheirreactivity,composition,or structure can be confusing or even meaningless. However, a very general NanoscaleInorganicPolyoxometalateClusters 3 approach has been adopted in order to help the researchers make the nec- essary connections between the different building block types, archetypes, andphysicalproperties.Fig.1presentsaverybroadclassificationofthepoly- oxometalate family which structurally and compositionally can be broken into three subcategories. (a) The first general category consists of the heteropolyanionic species which are constructed by a vanadium-, tungsten-, or molybdenum- based metal oxide framework and incorporates heteroanions such as PO 3(cid:1),SO 2(cid:1),SiO 2(cid:1),etc.Thissubgroupisbyfarthemostexplored 4 4 4 subsetofPOMclusterswithawiderangeofstructuralarchetypesdue totheinherentstabilityofthegeneratedbuildingblocklibrarieswhich arisesbytheincorporationofheteroanions.Thisisthemainreasonthat a lot of previous research focused on the modulation of catalytic, electronic, and acidic properties of these species with great emphasis on the Keggin [XM O ]n(cid:1) and the Wells–Dawson [X M O ]n(cid:1) 12 40 2 18 62 (where M¼W or Mo and X¼PO 3(cid:1), SO 2(cid:1), SiO 2(cid:1), etc.) anions. 4 4 4 Moreover, the kinetic inertness of tungsten-based POMs has given the opportunity for the development of Keggin- and Dawson-based Iso-POMs Hetero-POMs W 10 W 19 XM XM 10 12 W 11 W 22 W36 W34 X2M18 X5M30 Mo-Blues Mo-Brown Mo150 Mo132 Fig.1 Classificationofpolyoxometalateclusters.Themetaloxygenframeworkisshown ingraysticks(M,gray;O,red).Theheteroatomsareshownasorangetetrahedra. 4 H.N.Mirasetal. derivatives(mostcommonaremono-,di-,andtrilacunaryclusters)that can be used as stable building blocks for the construction of larger aggregatesinacontrollablefashion(13).Thedevelopmentoflacunary {M12(cid:1)n}andDawson{M18(cid:1)n},tungsten-basedpolyoxometalatesisa largearea;however,someguidingprincipleswillbediscussedtoallow the critical evaluation of the literature. (b) The second subset of the POM family consists of the isopolyanions where they are composed of a metal oxide framework without the incorporation of heteroatoms or heteroanions. Consequently, the membersofthissubsetaremuchsmallerduetothelessrobuststructural motifs than their heteropolyanion counterparts. However, they also have interesting physical properties, while they can also be used as cluster-based building blocks in a similar manner (14). (c) Finally there is a third category which consists of molybdenum-based reduced POM nanosized clusters, namely, Mo-blue and Mo-brown species. These clusters have been reported for the first time in 1783 by Scheele. However, due to their gigantic size, their composition andcomplexstructuralfeatureswereextremelychallengingbackthen tobedeterminedbytheavailableX-raydiffractioninstruments.Thus, their exceptional size and structural complexity remained unknown until Mu€ller et al. reported, in 1995, the synthesis and structural characterization of the first member of this subset which exhibited a ring topology and high nuclearity {Mo } (15). Following careful 154 exploration of the experimental variables of these systems led to the discovery and proper characterization of the first member of the Mo-brown species which exhibited a porous spherical topology {Mo } constructed by 132 molybdenum centers and higher extend 132 of reduction comparing to their Mo-blue counterparts (16). 2. FROM SERENDIPITY TO DIRECTED ASSEMBLY The synthesis of polyoxometalate species is usually described by a seriesofill-definedandconfusingtermssuchas“one-pot”orself-assembly regardingthesyntheticapproach.Thesetermsusuallydescribeonlythefinal outcome of a quite complicated network of interactive chemical processes giving the false impression of systems governed by simplicity, while the result is directed entirely by serendipitous and seemingly arbitrary events at the molecular level. The development in instrumentation and advances
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