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1、Articlepubs.acs.org/ICSynthesisandCharacterizationofNovelWells?Dawson-TypeMonoVanadium(V)-SubstitutedTungsto-polyoxometalateIsomers:1-and5?4?[S2VW17O62],?????§TadaharuUeda,*MihoOhnishi,MotooShiro,Jun-ichiNambu,ToshiakiYonemura,JohnF.Boas,∥andAlanM.Bond?DepartmentofAppliedScience,FacultyofScienc
2、e,KochiUniversity,Kochi780-8520,Japan?X-rayResearchLaboratory,RigakuCorporation,Akishima,Tokyo196-8666,Japan§SchoolofPhysics,MonashUniversity,Clayton,Victoria3800,Australia∥SchoolofChemistry,MonashUniversity,Clayton,Victoria3800,Australia*SSupportingInformationABSTRACT:Twovanadium(V)-substitute
3、dtungsto-polyoxo-metalateisomers,1-and4-[SVWO]5?,werepreparedas21762theirtetra-alkylammoniumsaltsfromaWVI?HSO?VV24reactionmixtureinaqueousCH3CNsolution.X-raycrystallo-graphicstructuralanalysisrevealedthatbothisomershaveaWells?Dawson-typestructurewithahigheroccupancyofvanadiumatpolarsitesandbelt
4、sitesfor1-and4-[SVWO]5?,respectively.21762Theisomerswerealsocharacterizedbyelementalanalysis,infrared,Raman,UV?vis,and51VNMRspectroscopiesaswellasvoltammetry,andthedataobtainedwerecomparedwiththatderivedfrom[SWO]4?.Signi?cantly,thereversible21862potentialsforthevanadium(V/IV)coupleforboth1-and4
5、-[SVWO]5?inCHCN(0.1Mn-BuNPF)areconsiderably21762346morepositivethanthetungstatereductionprocessexhibitedbythe[SWO]4?framework,implyingthatthepresenceof21862vanadiumshouldbeusefulincatalyticreactions.Theone-electron-reduced[SVIVWO]6?formsofbothisomerswere21762preparedinsolutionbycontrolledpotent
6、ialbulkelectrolysisandcharacterizedbyvoltammetryandEPRspectroscopy.■INTRODUCTIONtobeexcellentcatalystsforfacilitationofoxidationreactionsin5?11,14organicsyntheses.PolyoxometalateshavebeenextensivelystudiedforalongperiodPolyoxometalatesusuallyalsocontainaheteroioninacentraloftimebecauseoftheirpr
7、acticalapplicationsincatalysis,151?4positionwithintheframework.Themostwidelystudiedonesanalyticalchemistry,biochemistry,andother?elds.Recently,haveusedsilicateorphosphateforthispurpose.Otherheterointerestalsohasbeenfocusedontheiru
