Table Of Content

Editedby HeTianandJunjiZhang PhotochromicMaterials EditedbyHeTianandJunjiZhang Photochromic Materials Preparation,PropertiesandApplications Editors AllbookspublishedbyWiley-VCH arecarefullyproduced.Nevertheless, Dr.HeTian authors,editors,andpublisherdonot EastChinaUniversityofScience warranttheinformationcontainedin andTechnology thesebooks,includingthisbook,to KeyLaboratoryforAdvancedMaterials befreeoferrors.Readersareadvised 200237Shanghai tokeepinmindthatstatements,data, China illustrations,proceduraldetailsorother itemsmayinadvertentlybeinaccurate. Dr.JunjiZhang EastChinaUniversityofScienceand LibraryofCongressCardNo.:appliedfor Technology KeyLaboratoryforAdvancedMaterials BritishLibraryCataloguing-in-Publication 200237Shanghai Data China Acataloguerecordforthisbookis availablefromtheBritishLibrary. Cover ImgramPublishing,UK Bibliographicinformationpublishedbythe DeutscheNationalbibliothek TheDeutscheNationalbibliothek liststhispublicationintheDeutsche Nationalbibliografie;detailed bibliographicdataareavailableonthe Internetat<http://dnb.d-nb.de>. ©2016Wiley-VCHVerlagGmbH&Co. KGaA,Boschstr.12,69469Weinheim, Germany Allrightsreserved(includingthoseof translationintootherlanguages).No partofthisbookmaybereproducedin anyform – byphotoprinting, microfilm,oranyothermeans – nor transmittedortranslatedintoamachine languagewithoutwrittenpermission fromthepublishers.Registerednames, trademarks,etc.usedinthisbook,even whennotspecificallymarkedassuch, arenottobeconsideredunprotected bylaw. PrintISBN:978-3-527-33779-8 ePDFISBN:978-3-527-68370-3 ePubISBN:978-3-527-68372-7 MobiISBN:978-3-527-68371-0 oBookISBN:978-3-527-68373-4 CoverDesign SchulzGrafik-Design, Fußgönheim,Germany Typesetting SPiGlobal,Chennai,India PrintingandBinding Printedonacid-freepaper V Contents ListofContributors XI 1 Introduction:OrganicPhotochromicMolecules 1 KeitaroNakatani,JonathanPiard,PeiYu,andRémiMétivier 1.1 PhotochromicSystems 1 1.1.1 GeneralIntroduction 1 1.1.2 BasicPrinciples 4 1.1.3 PhotochromicMolecules:SomeHistory 5 1.2 OrganicPhotochromicMolecules:MainFamilies 8 1.2.1 ProtonTransfer 9 1.2.2 Trans–CisPhotoisomerization 12 1.2.3 HomolyticCleavage 13 1.2.4 CyclizationReaction 14 1.2.4.1 Spiropyrans,Spirooxazines,andChromenes 14 1.2.4.2 FulgidesandFulgimides 17 1.2.4.3 Diarylethenes 18 1.3 MolecularDesigntoImprovethePerformance 20 1.3.1 FiguresofMerit 20 1.3.2 FatigueResistance:IncreasingtheNumberofOperatingCycles 21 1.3.3 Bistability:AvoidingUnwantedThermalBack-Reactioninthe Dark 23 1.3.3.1 InfluenceofEthenicBridgeontheThermalStabilityoftheB Form 24 1.3.3.2 ImpactoftheHeteroarylSubstituentsontheThermalStabilityofthe BForm 24 1.3.4 FastPhotochromicSystems:RevertingBackSpontaneouslytothe ColorlessStateinaGlance 25 1.3.5 GainingEfficiencyofthePhotoreaction:theExampleof Diarylethenes 26 1.4 Conclusion 31 IrradiationataSpecificWavelength:IsosbesticPoint 32 VI Contents CaseA:WhentheThermalBack-ReactionisNegligibleComparedto thePhotochemicalReaction(TypicallyP-type) 33 CaseB:WhentheThermalBack-ReactionisMoreEfficientthanthe PhotochemicalB→AReaction(TypicallyType) 34 References 34 2 PhotochromicTransitionalMetalComplexesfor Photosensitization 47 Chi-ChiuKoandVivianWing-WahYam 2.1 Introduction 47 2.2 PhotosensitizationofStilbene-andAzo-ContainingLigands 48 2.3 PhotosensitizationofSpirooxazine-ContainingLigands 51 2.4 PhotosensitizationofDiarylethene-ContainingLigands 54 2.5 PhotosensitizationofPhotochromicN∧C-Chelate Organoboranes 63 2.6 Conclusion 65 References 66 3 Multi-addressablePhotochromicMaterials 71 ShangjunChen,WenlongLi,andWeihongZhu 3.1 MolecularLogicGates 71 3.1.1 Two-InputLogicGates 71 3.1.2 CombinatorialLogicSystems 74 3.1.2.1 Half-AdderandHalf-Subtractor 74 3.1.2.2 KeypadLocks 77 3.1.2.3 DigitalEncoderandDecoder 82 3.2 DataStorageandMolecularMemory 84 3.2.1 FluorescenceSpectroscopy 85 3.2.2 InfraredSpectroscopy 90 3.2.3 OpticalRotation 92 3.3 GatedPhotochromores 95 3.3.1 HydrogenBonding 95 3.3.2 Coordination 98 3.3.3 ChemicalReaction 99 References 105 4 PhotoswitchableSupramolecularSystems 109 GuangleiLv,LiangChen,HaichuangLan,andTaoYi 4.1 Introduction 109 4.2 PhotoreversibleAmphiphilicSystems 110 4.2.1 PhotoreversibleDiarylethene-BasedAmphiphilicSystem 110 4.2.2 PhotoreversibleAzobenzene-BasedAmphiphilicSystem 116 4.2.3 PhotoreversibleSpiropyran-BasedAmphiphilicSystem 119 4.3 PhotoswitchableHost–GuestSystems 122 4.3.1 PhotocontrolledSupramolecularSelf-Assembly 123 Contents VII 4.3.2 PhotocontrolledCaptureandReleaseofGuestMolecules 128 4.3.3 FluorescentSwitchingPromotedbyHost–GuestInteraction 133 4.3.4 PhotoswitchableMolecularDevices 137 4.4 PhotochromicMetalComplexesandSensors 141 4.4.1 MetalComplexeswithAzobenzeneGroups 141 4.4.2 MetalComplexeswithDiaryletheneGroups 144 4.4.3 MetalComplexeswithSpirocyclicGroups 150 4.4.4 MetalComplexeswithRhodamine 152 4.5 OtherLight-ModulatedSupramolecularInteractions 153 4.6 ConclusionsandOutlook 159 References 159 5 Light-GatedChemicalReactionsandCatalyticProcesses 167 RobertGöstl,AnttiSenf,andStefanHecht 5.1 Introduction 167 5.2 GeneralDesignConsiderations 169 5.3 PhotoswitchableStoichiometricProcesses 171 5.3.1 StartingMaterialControl 172 5.3.2 ProductControl 175 5.3.3 StartingMaterialandProductControl 177 5.3.4 TemplateControl 178 5.4 PhotoswitchableCatalyticProcesses 182 5.4.1 ActivityControl 182 5.4.2 SelectivityControl 185 5.5 Outlook 187 References 190 6 SurfaceandInterfacialPhotoswitches 195 JunjiZhangandHeTian 6.1 PhotochromicSAMs 196 6.1.1 PhotochromicElectrodeSAMs 196 6.1.2 PhotoreversibleFunctionalSurfaces 198 6.1.2.1 PhotoswitchableSurfaceWettability 198 6.1.2.2 PhotocontrolledCapture-and-ReleaseSystem 202 6.1.2.3 SmartPhotochromicSurfaceBasedonSupramolecular Systems 203 6.1.2.4 PhotochromicSurfaceforMolecularDataProcessing 205 6.2 PhotoregulatedNanoparticles 206 6.2.1 PhotochromicSwitchesonTraditionalMetalNanoparticles 208 6.2.1.1 PhotoswitchingontheMetalNanoparticles 208 6.2.1.2 PhotoinducedReversibleAggregationofNanoparticlesandTheir VersatileApplications 210 6.2.2 PhotochromicSwitchesonOtherNovelFunctional Nanoparticles 215 6.2.2.1 PhotoswitchableMagneticNanoparticles 215 VIII Contents 6.2.2.2 PhotomanipulatedQuantumDots 215 6.2.2.3 PhotochromicwithUpconversionNanoparticles 218 6.2.3 PhotocontrolledMesoporousSilicaNanoparticles 220 6.2.3.1 Photo-nanovalves 220 6.2.3.2 Photo-nanoimpellers 223 6.2.3.3 NIRLight-TriggeredMSNDrugDeliveryandTherapeutic Systems 224 6.3 PhotocontrolledSurfaceConductance 226 6.3.1 PhotochromicConductanceSwitchingBasedonSAMs 226 6.3.2 PhotochromicConductanceonSingle-MoleculeLevel 228 References 231 7 HybridOrganic/PhotochromicApproachestoGenerate MultifunctionalMaterials,Interfaces,andDevices 243 EmanueleOrgiuandPaoloSamorì 7.1 Introduction 243 7.1.1 TuningtheChargeInjectioninOrganic-BasedDevicesbyMeansof PhotochromicMolecules 245 7.2 TuningthePolaronicTransportinOrganicSemiconductorsby MeansofPhotochromicMolecules 251 7.2.1 PhotochromicMoleculesandOrganicSemiconductorsIncorporated inDyads,Multiads,andPolymers 251 7.2.2 TheMultilayerApproach 254 7.2.3 TheBlendingApproach 255 7.3 PhotoresponsiveDielectricInterfacesandBulk 262 7.4 ConclusionsandFutureOutlooks 267 Acknowledgments 268 References 268 8 PhotochromicBulkMaterials 281 MasakazuMorimoto,SeiyaKobatake,MasahiroIrie,HariKrishnaBisoyi, QuanLi,ShengWang,andHeTian 8.1 PhotochromicPolymers 281 8.1.1 GlassTransitionTemperature 281 8.1.2 Fluorescence 283 8.1.3 Conductivity 287 8.1.4 LivingRadicalPolymerization 288 8.1.5 SurfaceReliefGrating 290 8.1.6 PhotomechanicalEffect 290 8.2 Single-CrystallinePhotoswitches 293 8.2.1 Crystalline-StatePhotochromicMaterials 293 8.2.2 PhotochromicDiaryletheneSingleCrystals 293 8.2.3 InsituX-rayCrystallographicAnalysisofPhotoisomerization Reaction 295 8.2.4 PhotoisomerizationQuantumYields 296 Contents IX 8.2.5 MulticolorPhotochromismofMulticomponentCrystals 297 8.2.6 NanoperiodicStructuresFabricatedbyPhotochromic Reactions 299 8.2.7 PhotoinducedShapeChangesandMechanicalPerformance 301 8.3 PhotochromicLiquidCrystals 305 8.3.1 Introduction 305 8.3.2 Spiropyran-andSpirooxazine-BasedPhotochromicLiquid Crystals 309 8.3.3 Diarylethene-BasedPhotochromicLiquidCrystals 314 8.3.4 Azobenzene-BasedPhotochromicLiquidCrystals 320 8.3.5 OtherPhotochromicLiquidCrystals 327 8.3.6 ConclusionsandOutlook 328 8.4 PhotochromicGels 329 8.4.1 Introduction 329 8.4.2 AzobenzeneGels 330 8.4.3 SpiropyranandSpirooxazineGels 335 8.4.4 DiarylethenesGels 337 8.4.5 NaphthopyranGels 342 8.4.6 TheOtherPhotochromicGels 343 8.4.7 Conclusion 346 References 346 9 PhotochromicMaterialsinBiochemistry 361 DanielleWilsonandNeilR.Branda 9.1 Introduction 361 9.2 ReversiblePhotochemicalSwitchingofBiomaterialFunction 362 9.3 GeneralDesignStrategiesandConsiderations 362 9.3.1 PhotoswitchableTethers 364 9.3.1.1 TheIncorporationMethod 364 9.3.1.2 Considerations 364 9.3.2 PhotoswitchableSmallMolecules 365 9.3.2.1 TheIncorporationMethod 365 9.3.2.2 Considerations 365 9.3.3 ChromophoreSelection 367 9.4 SelectedExamples 367 9.4.1 PhotoswitchableEnzymes 367 9.4.1.1 Drug-InspiredSmallMoleculeInhibitors 367 9.4.1.2 PhosphoribosylIsomeraseInhibitorwithTwoBindingUnits 370 9.4.1.3 DirectModificationofEnzymeswithPhotochromicGroups 372 9.4.2 PhotoswitchablePeptidesandProteins 373 9.4.2.1 PeptideCross-Linking 373 9.4.2.2 CyclicAntimicrobialPeptide 375 9.4.2.3 GeneticallyEncodedAminoAcids 376 9.4.2.4 ControlofMotorProteinFunctionUsingSite-Selective Mutation 377 X Contents 9.4.3 PhotoswitchableIonChannelsandReceptors 379 9.4.3.1 PhotocontrolofChannelActivationandDesensitizationwitha TetheredGlutamate 380 9.4.3.2 PhotocontrolofInsulinReleaseUsingaSmallMolecular Sulfonylurea 380 9.4.3.3 PhotocontrolofReceptorsUsingRedLight 381 9.4.4 PhotoswitchableNucleotides 382 9.4.4.1 Spiropyran-ModifiedOligonucleotideBackbones 382 9.4.4.2 ControllingRNADuplexHybridizationwithLight 384 9.4.4.3 Diarylethene-ModifiedOligonucleotides 385 9.5 Summary 386 References 386 10 IndustrialApplicationsandPerspectives 393 JunjiZhangandHeTian 10.1 IndustrializationandCommercializationofOrganicPhotochromic Materials 393 10.1.1 CommercializedT-typePhotochromicMaterials 395 10.1.2 CommercializedP-TypePhotochromicMaterials 398 10.2 PerspectivesforOrganicPhotochromicMaterials 399 References 409 Index 417