有机硼聚合物及其在光电、传感方面的应用

AdvancesintheSynthesisofOrganoboranePolymersforOptical,Electronic,andSensoryApplicationsFriederJa¨kle*DepartmentofChemistry,RutgersUniversityNewark,Newark,NewJersey07102ReceivedJanuary26,2010Contents1.Introduction39852.Main-ChainFunctionalizedOrganoboronPolymers39862.1.PolymerswithBoron-CarbonBondsintheMainChain39872.1.1.Boron-VinylLinkages39872.1.2.Boron-ArylandBoron-AlkynylLinkages39902.1.3.TransitionMetal-ContainingPolymers39922.1.4.TheoreticalStudies39942.2.PolymerswithBoron-HeteroatomBondsintheMainChain39952.2.1.Boron-OxygenLinkages39952.2.2.Boron-NitrogenLinkages39962.3.PolymerswithTetracoordinateBoronintheMainChain39983.Side-ChainFunctionalizedConjugatedOrganoboronPolymers40033.1.ConjugatedPolymerswithTriorganoboraneGroups40033.2.ConjugatedPolymerswithOrganoboraneGroupsLinkedbyHeteroatoms40073.2.1.SystemswithTricoordinateBoron40073.2.2.SystemswithTetracoordinateBoron40073.3.BoronicAcid-FunctionalizedConjugatedPolymers40083.3.1.ElectrochemicalPolymerization40083.3.2.ChemicalandEnzymaticPolymerization40083.3.3.CompositesandHigher-OrderStructures40094.NonconjugatedPolymersFunctionalizedwithOrganoboraneChromophores40094.1.PolymerswithTricoordinateOrganoboranePendantGroups40104.2.PolymerswithTetracoordinateOrganoboranePendantGroups40114.3.PolymerswithTerminalBoraneChromophores40135.SelectedApplications40145.1.OpticalandElectronicDeviceMaterials40145.2.DetectionofAnionsandNeutralLewisBasicSubstrates40155.2.1.AnionRecognition40155.2.2.RecognitionofAmines40175.3.DetectionofPolyolswithBoronicAcid-FunctionalizedPolymers40175.3.1.ChangeinOpticalProperties40185.3.2.ChangeinConductivity40185.4.OtherDetectionMechanisms40186.ConcludingRemarks40197.Acknowledgments40198.References40191.IntroductionThepastdecadehaswitnessedrenewedinterestandnumerousunexpecteddiscoveriesintheareaofmaingrouporganometallicchemistry.Unusualbondingmodeshavebeenuncovered,1-4newmaterialshavebeendeveloped,5,6andnewapplicationsarebeingpursued.7-12Withrespecttonewmaterialswithunusualproperties,anexcitingfieldisthedevelopmentofhybridpolymersthatcombinemaingroupelementswithtypicalorganicstructuresinoneframework.13,14Amongmaingrouporganic-inorganichybridpolymers,thoseinvolvingGroup14andGroup15elementshavereceivedtremendousattentionoverthepastseveraldecades,withsilicones,polysilanes,andpolyphosphazenesamongthemostthoroughlystudiedmaterials.15-17Avarietyofotherclassesofnewpolymerscontainingnotonlysiliconandphosphorus,18-22butalsotheheavierhomologues,suchasgermanium,tin,arsenic,andantimonyhavebeenintroducedmorerecently.23-26Incomparison,organometallicpolymersthatcontaintheGroup13elementboron27-32haveuntilrecentlybeenfarlesswellestablished,despitepotentiallyintriguingpropertiesassociatedwiththeelectron-deficientnatureofmanyboroncompounds.Theinitiallyratherslowdevelopmentofthisfieldisprimarilyaresultofsyntheticdifficultiesencounteredatthetime:thehydrolyticandoxidativesensitivityofmanyboron-containingmoleculeswasregardedasanobstacleinthepursuitoftheirincorporationintopolymericstructures.However,morerecentachievementsoverthepastdecadeclearlydemonstratenotonlythatboron-containingpolymersofhighmolecularweightcanbeobtainedreadily,butalsothatmanyofthenewmaterialsareperfectlystableforextendedperiodsoftimeunderambientorevenforcingconditions.Inaddition,morecomplexpolymerarchitecturesincludingtelechelic(end-groupfunctionalized)polymersandblockcopolymerscannowberealizedthroughcontrolled/livingpolymerizationtechniques,providinganentrytoboron-containingnanostructuredmaterials.Theseremarkableadvancesweremadepossiblefortwospecificreasons.(1)Newsyntheticprocedureshavebeendevelopedincludingmildhydroborationandtransition-metalcatalyzedcouplingprocesses,controlledradicalpolymerizationtechniques,andhighlyselectivepolymermodificationmethods,justtonameafew.(2)Equallyimportantisthatseveralapproachesforstabilizationoftheresultingpolymersweresuccessfullyintroduced.Forinstance,theattachmentofbulkymesityl*Fax:[phone].E-mail:[e-mail].2010,110,3985–4022398510.1021/cr100026f2010AmericanChemicalSocietyPublishedonWeb06/10/2010(2,4,6-trimethylphenyl)ortripyl(2,4,6-triisopropylphenyl)groupstoboronturnedotherwisehighlyairandmoisture-sensitiveorganoboranepolymersintomaterialsthatcanbehandledwithoutanyspecialprecautions.Inaddition,incor-porationofboronintocyclicorheterocyclicstructures,suchasdiborazane,diazaborole,pyrazabole,8-hydroxyquinolatoborane,orBODIPYprovedtohavearemarkablestabilizingeffect.Thedevelopmentoftransitionmetal-catalyzedcou-plingofboron-containingmonomersmayservetofurtherillustratethispoint:Notonlyhaseverymajortransition-metalcatalyzedC-Cbondformingreactionnowbeensuccessfullyutilizedinthepreparationofboron-containingpolymers,itturnsoutthatevenSuzuki-Miyauracouplingreactionsthatarebasedonthecleavageofboronicacidgroupscanbeenappliedincertaincases!Whilethesyntheticadvancesoverthepastdecadehavebeentremendous,evenmoreimportantistoemphasizethatunusualandinterestingpropertiescanberealizedthatspecificallyrelyonthepresenceofboroninthemacromo-lecularstructure