联吡啶类电致变色材料的合成及器件(硕士学位论文)-副本

分类号：O69密级：公开档案号：2014-06-09-081704-24-012学号：1111091012硕士学位论文(学术学位）含联吡啶类电致变色材料的制备与全固态器件性能研究学生姓名：指导教师姓名：学科门类：工学专业名称：应用化学研究方向：材料化学及其应用二〇一四年六月含联吡啶类电致变色材料的制备与全固态器件性能研究学生姓名：指导教师姓名：专业名称：应用化学PreparationoftheElectrochromicMaterialsContainingBipyridineDerivativesandPropertiesoftheSolid-stateDevicesMasterCandidate:Supervisor:ProfessorMajor:AppliedChemistryJune,2014摘要摘要联吡啶类有机电致变色材料因其丰富的色彩和较快的颜色转换速度成为当前绿色光电材料的研究热点。本文以4,4’-联吡啶和取代三联吡啶为前驱体，合成了4类不同类型的联吡啶化合物，共计13个目标化合物，并对其结构做了表征。运用紫外和电化学分析了各化合物的光电性质和电致变色机理。结果表明：小分子紫精是通过氧化还原使分子结构在苯式和醌式间相互转换实现电致变色的，而联吡啶金属配合物的电致变色则是通过金属离子与配体间电荷迁移来实现的。分别通过旋转涂布和电化学沉积法在ITO导电玻璃上制备了联吡啶化合物的电致变色薄膜，并对其光电性能做了测试。以LiClO4-PMMA/PEO聚合物电解质为PE层制作了基于ITO玻璃的全固态电致变色器件，对器件的性能进行了测试。结果表明：以4,4’-双三苯胺紫精为EC材料的电致变色能够在0~-0.8V之间实现由无色到蓝绿色的可逆变化；以联吡啶的Fe(Ⅱ)配合物和Ru(Ⅱ)配合物为EC材料的电致变色器件在0~3V之间分别能够实现由紫色到蓝绿色和由橙红色到绿色的可逆变化。所有器件在不超过3V的驱动电压下，可以在着色和褪色两种状态下稳定可逆变化，着色/褪色时间响应较快，开路记忆时间长达300min，说明本文所制备的器件均具有优良的电致变色性能，有望制作实用的电致变色器件。关键词：联吡啶紫精电致变色循环伏安固体电解质全固态电致变色器件Abstract参考文献参考文献[1]李天文,刘鸿生.变色材料的研究与应用.[J].现代化工.2004.24(2):62.[2]代富平.全固态电致变色器件(WO3/SPE/NiOx)的制备与研究.[硕士学位论文].兰州:兰州大学,2002.[3]DR.Rosseinsky,RJ.Mortimer.ElectrochromicsystemsandtheProspectsfordevices.[J].Adv.Mater.2001.13:783-793.[4]D.W.Steuerman,H.R.Tseng,A.J.Peters,etal.Molecular-MechanicalSwitch-BasedSolid-StateElectrochromicDevices.[J].Angew.Chem.Int.Ed.2004.43:6486-6491.[5]B.Gorodetsky,N.R.Branda.BidirectionalRing-OpeningandRing-ClosingofCationic1,2-DithienylcyclopenteneMolecularSwitchesTriggeredwithLightorElectricity.[J].Adv.Funct.Mater.2007.17(5):786-796.[6]C.Xiong,A.E.Aliev,B.Gnade,etal.FabricationofSilverVanadiumOxideandV2O5NanowiresforElectrochromics.[J].ACSNano.2008,2(2):293-301.[7]T.T.To,C.B.Duke,C.S.Junker,etal.LinkageIsomerizationasaMechanismforPhotochromicMaterials:CyclopentadienylmanganeseTricarbonylDerivativeswithChelatableFunctionalGroups.[J].Organometallics2008.27(2):289-296.[8]V.F.Traven,A.Y.Bochkov,M.M.Krayushkin,etal.Coumarinyl(thienyl)thiazoles: NovelPhotochromeswithModulatedFluorescence.[J].Org.Lett.2008.10(6):1319-1322.[9]D.Pijper,M.G.M.Jongejan,A.Meetsma,etal.Light-ControlledSupramolecularHelicityofaLiquidCrystallinePhaseUsingaHelicalPolymerFunctionalizedwithaSingleChiropticalMolecularSwitch.[J].J.Am.Chem.Soc.2008.130(13):4541-4552.[10]C.W.Kim,S.W.Oh,Y.H.Kim,etal.CharacterizationoftheSpironaphthooxazineDopedPhotochromicGlass:TheEffectofMatrixPolarityandPoreSize.[J].J.Phys.Chem.C,2008.112(4):1140-145.[11]H.J.Kim,J.H.Jang,H.Choi,etal.PhotoregulatedFluorescenceSwitchinginAxiallyCoordinatedTin(IV)PorphyrinicDithienylethene.[J].Inorg.Chem.2008.47(7):2411-2415.[12]沈庆月,陆春华,许仲梓.光致变色材料的研究与应用.[J].材料导报2005,19(10):31-35.[13]K.Ueno,K.Matsubara,M.Watanabe,Y.Takeoka.AnElectronicandThermochromicHydrogelasaFull-ColorIndicator.[J].Adv.Mater.2007.19:2807-2812.[14]J.Harada,T.Fujiwara,K.Ogawa.CrucialRoleofFluorescenceintheSolid-StateThermochromismofSalicylideneanilines.[J].J.Am.Chem.Soc.2007.129(51):16216-1622l.[15]C.S.Rodolfo,A.Layza,D.A.Mayela,R.G.Jorge.pH-andThermosensitivePolyanilineColloidalParticlesPreparedbyEnzymaticPolymerization.[J].Langmuir,2007.23(1):8-12.[16]S.Dei,A.Matsumoto,A.Matsumoto.ThermochromismofPolydiacetylenesintheSolidStateandinSolutionbytheSelf-OrganizationofPolymerChainsContainingNoPolarGroup.[J].Macromolecules2008.41(7):2467-2473.[17]M.Gaudon,.A.E.Thiry,A.Largeteau,etal.CharacterizationofthePiezochromicBehaviorofSomeMenlbersoftheCuMo1-xWxO4Series.[J].Inorg.Chem.2008.47(7):2404-2410.[18]Y.Sagara,T.Mutai,I.Yoshikawa,.K.Aiaki.MaterialDesignforPiezochromicLuminescence:Hydrogen-Bond-DirectedAssembliesofaPyreneDerivative.[J].J.Am.Chem.Soc.2007.129(6):1520-1521.[19]贾美琳,陈庆,王筱梅等.喹啉盐与吡啶盐花青染料分子酸致变色行为的研究.[J].信息记录材料,2009,10(5):13-16.[20]李天文,王向荣,和丽霞.机光色材料和热色材料的发展.[J].无机盐工业1995.27(3):13-27.[21]A.J.Boydston,P.D.Vu,O.L.Dykhno,etal.ModularFluorescentBenzobis(imidazolium)Salts:Syntheses,PhotophysicalAnalyses,andApplications.[J].J.Am.Chem.Soc.2008.130(10):3143-3156[22]A.A.Ishehenko,A.V.Kulinich,S.L.Bondarev,V.N.Knyukshto.PhotodynamicsofPolyene-PolymethineTransformationsandSpectralFluorescentpropertiesofMerocyanineDyes.[J].J.Phys.Chem.A,2007.111(51):13629-13637[23]王旭东,徐伟箭.可逆热致变色材料的应用新进展.[J].化工进展2000.3:42-45[24]李天文,刘鸿生.变色材料的研究与应用.[J].现代化工2004.24(2):62[25]PMS.Monk,RJ.Mortimer,DR.Rosseinsky.ElectrochrOmism:FundamentalsandApplications.[M],VCH,Weinheim1995.[26]P.Bonhote,E.Gogniat,F.Campus.Nanocrystallineelectrochromicdisplays.DisPlays.1999.20:137-144.[27]D.R.Rosseinsky,R.J.Mortimer.ElectrochromicSystemsandtheProspectsforDevices.Adv.Mater.2001.13(11):783-79.[28]O.Glenser,C.Naumann.KristallisierteWolframblauverbindungen;WasserstoffanalogaderWolframbronzenHxWO3.[J].Z.Anorg.Allg.Chem.1951.265:288.[29]M.G.Charlton.HydrogenReductionofTungstenTrioxide.[J]Nature,1952.169(19):109-110.[30]JohnR.Platt.\o"LinktoArticle"Electrochromism,aPossibleChangeofColorProducibleinDyesbyanElectricField.[J].J.Chem.Phys.1961.34(3):862.[31]S.K.Deb.Thereversiblecolouration-bleachingProcessintungstentrioxideunder.theactionofanapplied.electricfield.[J].Appl.Opt.Suppl.1969.3:193.[32]S.K.Deb.OpticalandPhotoelectricPropert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