聯(lián)吡啶類(lèi)電致變色材料的合成及器件(碩士學(xué)位論文)-副本

分類(lèi)號(hào)：O69密級(jí)：公開(kāi)檔案號(hào)：2014-06-09-081704-24-012學(xué)號(hào)：1111091012碩士學(xué)位論文(學(xué)術(shù)學(xué)位）含聯(lián)吡啶類(lèi)電致變色材料的制備與全固態(tài)器件性能研究學(xué)生姓名：指導(dǎo)教師姓名：學(xué)科門(mén)類(lèi)：工學(xué)專(zhuān)業(yè)名稱(chēng)：應(yīng)用化學(xué)研究方向：材料化學(xué)及其應(yīng)用二〇一四年六月含聯(lián)吡啶類(lèi)電致變色材料的制備與全固態(tài)器件性能研究學(xué)生姓名：指導(dǎo)教師姓名：專(zhuān)業(yè)名稱(chēng)：應(yīng)用化學(xué)PreparationoftheElectrochromicMaterialsContainingBipyridineDerivativesandPropertiesoftheSolid-stateDevicesMasterCandidate:Supervisor:ProfessorMajor:AppliedChemistryJune,2014摘要摘要聯(lián)吡啶類(lèi)有機(jī)電致變色材料因其豐富的色彩和較快的顏色轉(zhuǎn)換速度成為當(dāng)前綠色光電材料的研究熱點(diǎn)。本文以4,4’-聯(lián)吡啶和取代三聯(lián)吡啶為前驅(qū)體，合成了4類(lèi)不同類(lèi)型的聯(lián)吡啶化合物，共計(jì)13個(gè)目標(biāo)化合物，并對(duì)其結(jié)構(gòu)做了表征。運(yùn)用紫外和電化學(xué)分析了各化合物的光電性質(zhì)和電致變色機(jī)理。結(jié)果表明：小分子紫精是通過(guò)氧化還原使分子結(jié)構(gòu)在苯式和醌式間相互轉(zhuǎn)換實(shí)現(xiàn)電致變色的，而聯(lián)吡啶金屬配合物的電致變色則是通過(guò)金屬離子與配體間電荷遷移來(lái)實(shí)現(xiàn)的。分別通過(guò)旋轉(zhuǎn)涂布和電化學(xué)沉積法在ITO導(dǎo)電玻璃上制備了聯(lián)吡啶化合物的電致變色薄膜，并對(duì)其光電性能做了測(cè)試。以LiClO4-PMMA/PEO聚合物電解質(zhì)為PE層制作了基于ITO玻璃的全固態(tài)電致變色器件，對(duì)器件的性能進(jìn)行了測(cè)試。結(jié)果表明：以4,4’-雙三苯胺紫精為EC材料的電致變色能夠在0~-0.8V之間實(shí)現(xiàn)由無(wú)色到藍(lán)綠色的可逆變化；以聯(lián)吡啶的Fe(Ⅱ)配合物和Ru(Ⅱ)配合物為EC材料的電致變色器件在0~3V之間分別能夠?qū)崿F(xiàn)由紫色到藍(lán)綠色和由橙紅色到綠色的可逆變化。所有器件在不超過(guò)3V的驅(qū)動(dòng)電壓下，可以在著色和褪色兩種狀態(tài)下穩(wěn)定可逆變化，著色/褪色時(shí)間響應(yīng)較快，開(kāi)路記憶時(shí)間長(zhǎng)達(dá)300min，說(shuō)明本文所制備的器件均具有優(yōu)良的電致變色性能，有望制作實(shí)用的電致變色器件。關(guān)鍵詞：聯(lián)吡啶紫精電致變色循環(huán)伏安固體電解質(zhì)全固態(tài)電致變色器件Abstract參考文獻(xiàn)參考文獻(xiàn)[1]李天文,劉鴻生.變色材料的研究與應(yīng)用.[J].現(xiàn)代化工.2004.24(2):62.[2]代富平.全固態(tài)電致變色器件(WO3/SPE/NiOx)的制備與研究.[碩士學(xué)位論文].蘭州:蘭州大學(xué),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]沈慶月,陸春華,許仲梓.光致變色材料的研究與應(yīng)用.[J].材料導(dǎo)報(bào)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]賈美琳,陳慶,王筱梅等.喹啉鹽與吡啶鹽花青染料分子酸致變色行為的研究.[J].信息記錄材料,2009,10(5):13-16.[20]李天文,王向榮,和麗霞.機(jī)光色材料和熱色材料的發(fā)展.[J].無(wú)機(jī)鹽工業(yè)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]王旭東,徐偉箭.可逆熱致變色材料的應(yīng)用新進(jìn)展.[J].化工進(jìn)展2000.3:42-45[24]李天文,劉鴻生.變色材料的研究與應(yīng)用.[J].現(xiàn)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.OpticalandPhotoelectricPropertiesandColourCencresinThinFilmsofTungstenOxides.[J].Philos.Mag.1973.27:801-822.[33]S.K.Deb.[J].Opportunitiesandchallengesofelectrochromicphenomenaintransitionmetaloxides.Sol.Energ.Mat.Sol.C.1992.25(3-4):327–338.[34]C.J.Schoot,J.J.Ponjee,H.T.vanDam,etal.NewelectrochromicmemorydisPlay.[J].Appl.Phys.Lett.1973.23(2):64.[35]C.M.Lampert.Electrochromicmaterialsanddevicesforenergyefficientwindows.[J].Sol.Energ.Mat.1984,11(1-2):1-27.[36]C.M.Lampert.Innovativesolaropticalmaterials.[J].OpticalEngineering.1984.23(1):92[45]鏢崎研二等.日本索尼公司.[P].中國(guó)專(zhuān)利,2001,申請(qǐng)?zhí)?01808702.7.[37]U.Baeh,D.Corr,D.Lupo,etal.Nanomaterials-BasedElectroehromicsforPaper-QualityDisplays.[J].Adv.Mater.2002.14(11):845-848.[38]ComiskeyB,AlbertJD,YoshizawaH,eta1.Anelectrophoreticinkforall-printedreflectiveelectronicdisplays.[J].Nature.1998,394(16):253..[39]饒凱,全固態(tài)電致變色器件的研究.[碩士學(xué)位論文].重慶:西南師范大學(xué),2004.[40]馮博學(xué),陳沖,何毓陽(yáng)等.電致變色材料及器件的研究進(jìn)展[J].功能材料.2004.2(35):145-149.[41]丘思疇,黃漢堯,舒興勝等.電致變色材料及其應(yīng)用.[J].功能材料1994,25(2):104.[42]BWFanghnan,ElectrochromisminWO3amorphousfilms.[J].RCARev.1975,36(1):177.[43]E.Ozkan,L.Se-Hee,CEdwinTracy,etal.Comparisionofeleetrochromieaulorphousandcrystallinetungstenoxidefilms[J].Solar.Energ.Mat.Sol.C.2003,79:439.[44]CNtarajan,SOhkubo,GNogmi.Influenceoffilmprocessingtemperatureontheelectreehromicpropertiesofelectrodepesitednickelhydroxide[J].Rev.Chem.Miner.1984,21:487.[45]DKBenson,Opticalmaterialstechnologyforenergy[A].EfficiencyandsolarEnergyConversionVI.SPIE[C].1987,72:823.[46]MRezrazi,OBohnke,JPagetti.Electrochromiebehaviourofthinfilmsoftungstentrioxidepreparedbyanodicoxidationoftungstenwithpulsedcurrent[J].SolidStateIorries,1996,86-88(2):949.[47]PDelichere,PFalaras,MFroment.Preparationandphysicochemicalpropertiesoffilmsinthevirginandcolouredstates[J].ThinSolidFilms.1988,161:35.[48]HiroharuKawasaki,TsuyoshiUeda,YeshiakiSuda,PropertiesofmetaldopedtungstenOxidethinfilmsforNOxgasnsorsgrownbyPLDmethodcombinedwithsputteringprocess.[J].SensorsandActuators,2004,100:266.[49]孫艷.溶膠一凝膠法制電致致變色材料的研究.[院碩士學(xué)位論文].長(zhǎng)春:長(zhǎng)春光學(xué)精密機(jī)械學(xué)院,2001.[50]F.S.Han,M.Higuehi,D.G.Kurth.Metallo-SupramolecularPolymersBasedonFunctionalizedBis-terpyridinesasNovelElectroehromicMaterials.[J].Adv.Mater.2007.19:3928-3931.[51]Y.W.Zhong,N.Vila,J.C.Henderson,etal.DinuclearTransitionMetalTerpyridineComplexeswithaDithienylcyclo-PenteneBridgeDirectedtowardMolecularElectronic.Applications.[J].Inorg.Chem.2007.46(25):10470-10472.[52]W.S.Alencar,F.N.Crespilho,M.R.M.C.Santos,etal.InfluenceofFilmArchitectureontheCharge-TransferReactionsofMetallophthaloeyanineLayer-by-LayerFilms.[J].J.Phys.Chem.C,2007.111(34):12817-12821.[53]H.John,C.Briehn,J.Scllnlidt,etal.TrinclearCyanines(TNCs)Revisited:ANewClassofElectrochromicsbyIntramolecularπ/σSwitching.[J].Angew.Chem.Int.Ed.2007.46:449-453.[54]S.Hunig,C.A.Briehn,P.Banerle,A.Emge.ElectrochromicsbyIntramolecularRedoxSwitchingofSingleBonds.[J].Chem.Eur.J.2001.7(13):2745-275.[55]S.Hunig,A.Langels,M.Schmittel,etal.Violene/CyanineHybridsasElectrochromicSystems:ANewVariationoftheGeneralStructure.[J].Eur.J.Org.Chem.2001.1393-1399.[56]XGLi,HYWang,MRHuang.Synthesis,Film-Forming,andElectronicPropertiesofo-PhenylenediamineCopolymersDisplayingAnUncommonTricolor.[J].Macromolecules2007.40(5):1489-1496.[57]D.D.Longchamp,P.T.Hammond.Layer-by-LayerAssemblyofPEDOTPolyanilineElectrochromicDevices.[J].Adv.Mater.2001.13(19):1455-1459.[58]R.M.Walezak,J.H.Jung,J.S.Cowart,etal.3,4-Alkylenedioxyrrole-BasedConjugatedPolymerswithFinelyTunedElectronicandOpticalPropertiesviaaFlexibleandEfficientN-FunctionalizationMethod.[J].Macromolecules2007.40(22):7777-7785.[59]E.Unur,J.H.Jung,R.J.Mortimer,J.R.Reynolds.Dual-PolymerElectrochromicFilm.CharacterizationUsingBipotentiostaticControl.[J].Chem.Mater.2008.20(6):2328-2334.[60]G.E.Gunbas,A.Dunnus,L.Toppare.CouldGreenbeGreener?NovelDonor-Acceptor-TypeElectrochromicPolymers:TowardsExcellentNeutralGreenMaterialswithExceptionalTransmissiveOxidizedStatesforCompletionofRGBColorSpace.[J].Adv.Mater.2008.20:691-695.[61]C.R.G.Grenier,S.J.George,T.J.Joneheray,etal.ChiralEthylhexylSubstituentforOpticallyActiveAggregatesofπ-ConjugatedPolymers.[J].J.Am.Chem.Soc.2007.129(35):10695-10699.[62]A.L.Dyer,C.R.G.Grenier,J.R.Reynolds.APoly(3,4-alkylenedioxythiophene)ElectroehromicVariableOpticalAttenuatorwithNear-InfraredReflectivityTunedIndependentlyoftheVisibleRegion.[J].Adv.Funct.Mater.2007.17(9):1480-1486.[63]蔣慶龍,傅相鍇,陳祝君.烯烴取代的紫羅精合成及全固態(tài)電致變色器件.[J].應(yīng)用化學(xué),2007,24(9):1032-1035.[64]曹良成,王躍川.紫精類(lèi)電致變色材料的制備和機(jī)理.[J].化學(xué)進(jìn)展,2008,20(9):1353-1360.[65]CLBird,ATKuhn,Electrochemistryoftheviologens.[J].Chem.Soc.Rev.1981,10:49.[66]C.J.Schoot,J.J.Ponjee,HTVan,etal.Newelectrochromiememorydisplay.[J].Appl.PhysLett.1973,23:64.[67]姜建壯吳基培杜大明孫思修,三明治型金屬卟啉、酞菁配合物功能材.[J].大學(xué)化學(xué),1999,14(2):5.[68]GCSCollins,DJSchiffrin,Thepropertiesofelectrochromicfilmelectrodesoflanthanidedipthalocyaninesinethyleneglycol.[J].Electrochem.Soc.1985,132:1835.[69]JungS,KmH,HanM,etal.Layer-by-layerassemblyofPoly(aniline-N-butyl-sulfonate)sandtheirelectrochromicPropertiesinanallsolidstatewindow.[J].Mater.Sci.Eng.C.2004.24:57-60.[70R.B.Goldner,T.E.Haas,G.Seward,etal.Thinfilmsolidstateionicmaterialsforelectrochromicsmartwindowglass.[J].SolidStateIonics.1988.28-30(2):1715.[71]MichaelA.Invernale,YujieDing,GregoryA.Sotzing.All-OrganicElectrochromicSpandex.[J].J.Am.Chem.Soc.2010,2(1):296-300.[72]A.Peter,F.Robert,P.T.Printable.All-OrganicElectrochromicActive-MatrixDisplays.[J].Adv.Funct.Mater.2007,17:3074-3082.[73]AKaruppasamy,ASubrahmanyam.StudiesonelectrochromicsmartwindowsbasedontitaniumdopedWO3thinfilms.[J].ThinSolidFilms,2007,516(2-4),175-178.[74]GLiu,TJRichardson.Sb-Cu-Lielectrochromicmirrors.[J].Sol.Energ.Mat.Sol.C.2005,86(1):113.[75]Mamaha,TNakano,Y.Motokazu,etal.AstoragetypeElectrochromicdisplayutilizingpoly-Co-QTPPfilms.[J].Jpn.J.Appl.Phys.1987,26(7):1113.[76]CKaes,AKatz,MWHosseini.Bipyridine:themostwidelyusedligand.Areviewofmoleculescomprisingatleasttwo2,2'-bipyridineunits.[J].Chem.Rev.2000,100(10):3553.[77]P.R.Andres,U.S.Schubert.NewFunctionalPolymersandMaterialsBasedon2,2′:6′,2″-TerpyridineMetalComplexes.[J].Adv.Mater.2003,16(13):1043-1068.[78]H.Harald,U.S.Schubert.Recentdevelopmentsinthesupramolecularchemistryofterpyridine–metalcomplexes.[J].Chem.Soc.Rev.,2004,33,373-399.[79]CAFustin,BGGLohmeijer,ASDuwez,NanoporousThinFilmsfromSelf-AssembledMetallo-SupramolecularBlockCopolymers.[J].Adv.Mater.2005,17(9):1162-1165.[80]E.Migianu,M.Beley,K.Gilbert.SynthesisofNewTerpyridinesunderSolventlessConditionsUsingAlumina.[J].Synthesis,2004,2:267-270.[81]EtienneBaranoff,Jean-PaulCollin,LuciaFlamigni,Fromruthenium(II)toiridium(III):15yearsoftriadsbasedonbis-terpyridinecomplexes.[J].Chem.Soc.Rev.2004,33:147-155.[82]EdwinCConstable,2,2′:6′,2″-Terpyridines:fromchemicalobscuritytocommonsupramolecularmotifs.[J].Chem.Soc.Rev.2007,36:246-253.[83]GHMoon,KCSeok,GOSeong,etal.,PreparationandcharacterizationofpolyanilinenanoparticlessynthesizedformDBSAmicellarsolution.[J].Synth.Met.2002,126:53.[84]JidongZhang,FanliLu,HaichaoHuang,etal.,Nearinfraredelectrochromismoflutetiumphthalocyanine.[J].Synth.Met.2005,148:123.[85]李襄宏,含1,3,4.嗯二唑的聯(lián)吡啶釕(Ⅱ)配合物的合成及光電性質(zhì)研究.[J].無(wú)機(jī)化學(xué)學(xué)報(bào)2010,26(8):1389-1393.[86]FXCheng,.CXHe,MLRen,etal,Preparation,photophysical,andelectrochemicalpropertiesofthreetrinuclearRu(II)complexes:Bridgingligandscomposedof2,2’-bipyridineand4,5-diazafluorenefragments,Inorg.Chem.Commun.2014,43:10-14.[87]MichaelisL,HillES.TheViologenIndicators.[J].J.Gen.Phys