Photosensitization by reversible electron transfer- theories, experimental evidence, and examples.pdf

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1、Chem.Rev.1986,86,401-449401PhotosensitizationbyReversibleElectronTransfer:Theories,ExperimentalEvidence,andExamplesGEORGEJ.KAVARNOS'andNICHOLASJ.TURRO'ChemistryDepaHment,ColumbiaUniversi?y,NewYork,NewYork70027ReceivedAugust19,1985(RevisedManuscriptReceivedDecember26,1985)Contents2.Ele

2、ctronicEnergyLevels4183.QuenchingRateConstantsvs.the419I.Introduction401DrivingForceofElectronTransferA.Background402B.DetectionofIntermediates419B.ScopeoftheReview4031.FlashPhotolysisDetection41911.TheoreticalConcepts4042.ESRISpinTraps419A.AnOverviewofQuenchingPathways4043.CIDNP4191.

3、QuenchingviaEncounterComplexes4044.Luminescence4202.QuenchingviaExciplexes4055.FurtherStudiesofIntermediates4203.QuenchinginRigidIntramolecular406C.ProductStudies420Systems1.ScavengersofIntermediates4204.QuenchingbyHopping4062.StructureofProducts420B.Energetics4063.GenerationofInterme

4、diates4201.FreeEnergyChangesinPrimary406ElectronTransferD.Kinetics4202.FormationofRadicalIonsinSolution4071.QuenchingStudies4203.StabilizationofExciplexesandContact4072.MagneticFieldEffects420IonPairsE.TheEffectofSolventPolarity4204.TheRoleofEnergeticsandSolvent408IV.ExamplesofElectro

5、n-Transfer421PolarityinEnergyTransferPhotosensitizationC.ADynamicModelofPrimaryElectron409A.SpectroscopicandElectrochemical421TransferBasedupontheFranck-CondonPropertiesoftheSensitizer:PracticalPrincipleandtheClassicalTheoryofConsiderationsMarcusB.EvidencethatPrimaryQuenchingIsvia4211

6、.KineticandRateExpressions409ElectronTransfer2.ElectronicandNuclearTimeScalesin4101.QuenchingoftheExcitedStatesof421ElectronTransferMetalComplexes3.PotentialEnergySurfaces4102.QuenchingoftheExcitedStatesof4284.TheElectronicInteractionEnergy:410AromaticHydrocarbonsandKetonesbyAdiabatic

7、andNonadiabaticElectronAminesTransfer3.IntramolecularQuenchingbyElectron4315.ElectronicBarriers411Transfer6.NuclearBarriers412C.ReactionsPhotosensitizedbyElectron437Transfer7.UsefulKineticRelationshipsDerived414fromSelf-ExchangeElectron-Transfer1.ReactionsofAlkenes437Reactions2.BondCl

8、eavag