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第23卷 第1期Vol.23 No.1 JournalofMaterialsScience&Engineering总第93期Feb.2005:1004-793X(2005)01-0031-04:2004-03-24;:2004-05-21:(BK2004086):(1977-),,,,。,,,(, 210093) 【 】 4,8--1,5-(M-I)1,4--2,5-(M-Ⅱ)4,4′-(M-Ⅲ),HeckP-1、P-2。1H,13CNMR、、FT-IR、UV、。,,。P-1、P-2,。【】 ;;;Heck:TQ31 :ASynthesisandPropertiesofConjugatedPolymerIncorporatingNaphthaleneUnitsCHENLing-wu,SONGJin-feng,LIUTian-dong,CHENGYi-xiang(CollegeofChemistryandChemicalEngineering,NanjingUniversity,Nanjing 210093,China)【Abstract】 ConjugatedcopolymerP-1andP-2wereobtainedbythepolymerizationof4,8-dibromo-1,5-dibutoxynaphthalene(M-I)and1,4-divinyl-2,5-dibutoxybenzene(M-Ⅱ),4,8-dibromo-1,5-dibutoxynaphthalene(M-Ⅰ)and4,4′-divinylbiphenyl(M-Ⅲ)throughPd-catalyzedHeckreaction.BothmonomersandpolymerwerecharacterizedbyNMR,MS,FT-IR,UV,Cyclicvoltammetry,fluorescentspectroscopyandsoon.Naphthylunitisagoodchromophore.Thecopolymerspossessgoodsolubilityincommonsolventsduetothepresenceofalkoxylsubstituentsinthemolecularchains.ThecopolymersP-1andP-2canemitverystronggreenfluorescence.Theyareexpectedtohavepotentialapplicationinthematerialsofelectro-opticalmolecularsensors.【Keywords】 conjugatedpolymer;naphthalene;photoluminescence;heckreaction1 引 言PPV[1],。[2]:PPV,、,、。PPV[3]。,,,。HeckPPV,,,,。2 实验部分2.1 :1,5-;、、、、、。:SLM48000DSCF;Perkin-ElmerLambda25;1H,13CNMRBrukerDMX-300,TMS,CDCl3;CHI660;HN-O-RAPID;MicromassGCT;Nicolet-170SX。2.2 4,8--1,5-(M-Ⅰ)DOI:10.14136/j.cnki.issn1673-2812.2005.01.009(Scheme1)2.2.1 1,5-[7] 250mL,7.3g(0.046mol)1,5-,13.8g(0.101mol),18.9g(0.137mol),80mL,12h。,,,,,,,6.9g,55.2%。:103～106℃;1HNMR(CDCl3),δ:1.05(t,6H,J=7.33Hz),1.57～1.69(m,4H),1.89～1.98(m,4H),4.15(t,4H,J=6.26Hz),7.37(t,2H,J=8.00Hz),7.86(d,2H,J=8.40Hz);IR(KBr),σ/cm-1:1591.24,1509.96,1474.61,1417.90,1389.97,1266.21,1079.83,1062.91,1048.34,1018.29,775.01。2.2.2 4,8--1,5-(M-Ⅰ)[8] 100mL,1.83g(6.73mmol)1,5-,2.63g(14.8mmol)N-(NBS),50mL,24h,,CCl4,NBS,,CCl4,CH2Cl2,,,,CCl4,1.0g,34.4%。:140～142℃;1HNMR(CDCl3),δ:1.02(t,6H,J=7.37Hz),1.63(m,4H),1.96(m,4H),4.07(t,4H,J=6.43Hz),6.73(d,2H,J=8.70Hz),7.69(d,2H,J=8.40Hz);IR(KBr),σ/cm-1:1584.63,1510.60,1466.23,1362.09,1350.84,1305.94,1249.45,1054.87,1019.78,802.01。2.3 1,4--2,5-(M-Ⅱ)(Scheme2) 1,4-[9],1,4--2,Scheme1SynthesisrouteofM-Ⅰ 5-[7]。1,4-()-2,5-:100mL,4g(9.75mmol)1,4--2,5-,5.6g(21.4mmol)PPh330mL,4h,,,7.3g,80%。50mL,1.73g(1.85mmol)1,4-()-2,5-,27mL7.2mL,16mL20%,1h。50mL10mL,,10mL2,,2,,,50%20.27g,53.2%。:42～44℃;1HNMR(CDCl3),δ:1.01(t,6H,J=7.4Hz),1.48～1.61(m,4H),1.77～1.86(m,4H),4.00(t,4H,J=6.4Hz),5.28(d,2H,J=10.9,1.3Hz),5.76(d,2H,J=17.7,1.3Hz),7.01(s,2H),7.10(dd,2H,J=8.9,6.6Hz);13CNMR(CDCl3),δ:14.31,19.78,30.11,31.95,69.39,110.90,114.40,127.57,131.94,151.03;IR(KBr),σ/cm-1:2959.1,2934.1,2871.8,1621.6,1497.8,1425.7,1378.9,1204.6,1068.5,1027.4,994.3,903.2;HRMS(m/z):274(M+,42.56),162(100)。Scheme2SynthesisrouteofM-Ⅱ 2.4 4,4′-(M-Ⅲ)(Scheme3)2.4.1 4,4′-[10] 100mL,4g(25.9mmol),4g(0.133mol),10mLHBr,5mL85%H3PO4,30mLHOAc,HBr1h,80℃,,,,,,,,,。7.4g,84%。:162～170℃;1HNMR(CDCl3),δ:4.58(s,4H),7.50(d,4H,J=8.06Hz),7.59(d,4H,J=8.07Hz);13CNMR(CDCl3),δ:33.7,127.91,130.00,137.53,140.95;IR(KBr),σ/cm-1:1494.51,1441.96,1398.60,1274.10,1121.00,1004.74,824.67,803.31,728.46,677.50。2.4.2 4,4′-() 100mL,5.6g(16.4mmol)4,4′-,6g(22.9mmol)PPh3,30mLN,N-(DMF),,3,,,,,。2.4.3 4,4′-(M-Ⅲ)[11] 50mL,4.5g(5.2mmol)4,4′-,20mL16mL,16mL(20g)9%·32· 20052,3。,50mL10mL,,10mL,2,,2,,,50%20.86g,80%。:148～152℃;1HNMR(CDCl3),δ:5.30(d,2H,J=10.9Hz),5.82(d,2H,J=19.8Hz),6.78(dd,2H,J=17.5,J=6.6Hz),7.51(d,4H,J=8.1Hz),7.60(d,4H,J=8.1Hz);13CNMR(CDCl3),δ:114.31,127.05,127.40,136.77,137.05,140.45;IR(KBr),σ/cm-1:1626.1,1497.6,1397.2,991.3,903.1,829.5:HRMS(m/z):206(100)。Scheme3SynthesisrouteofM-Ⅲ 2.5 [9,12](Scheme4)2.5.1 P-1 25mL,202mg(0.47mmol)4,8--1,5-(M-Ⅰ),113.7mg(0.47mmol),1,4--2,5-(M-Ⅱ),3.3mg(0.019)PdCl2,30mg(0.114mmol),8mLN,N-,1mL,115℃,12h,140℃2h。,200mL,,,,,,60%。2.5.2 P-2 ,,65%。Scheme4SynthesisrouteofP-1 ,,P-1P-2THF、CH2Cl2、CHCl3、DMF,、、。Scheme5SynthesisrouteofP-2 3 结果与讨论3.1 UV-VisP-1、P-21,260～450nm,P-1、P-2π-π＊,335、330nm。,(HOMO)(LUMO)(Eg),,-λonset,λonsetEg[13,14]。P-1λonset475nm,Eg2.61eV;P-2λonset382nm,Eg3.25eV。3.2 P-1、P-223,P-1493496nm;P-2468475nm。P-1、P-21 P-1、P-2(THF)Fig.1 UV-visspectraofP-1andP-2(inTHF),,,[13,14]。3.3 CH3CN,Bu4NPF6,·33·231,. 2 P-1Fig.2 SolidandsolutionphotoluminescencespectraofP-1(inTHF,λex=425nm;Solid,λex=397nm)3 P-2Fig.3 SolidandsolutionphotoluminescencespectraofP-2(inTHF,λex=391nm;Solid,λex=410nm)Pt(=1mm),Pt,(SCE),(FOC),50mV/s。HOMOLUMOEonset(red)Eonset(ox),,(EHOMO(FOC)=4.8eV),,HOMOLUMO[14]:EHOMO=Eonset(ox)+4.8-EFOC;ELUMO=EHOMO-Eg。45,Eonset(ox)0.34V,P-1Eonset(ox)1.47V,EHOMO-5.93eV;P-1Eg2.61eV,ELUMO-3.32eV[15]。P-2Eonset(ox)1.56V,P-2Eg3.25eV,P-2EHOMO-6.02eV,ELUMO-2.77eV。HOMOLUMO,、,[16]。4 结 论1.,P-1、P-2THF、CH2Cl2、CHCl3、DMF。2.PPV,P-1、P-2。4 P-1Fig.4 CyclicvoltammogramofP-1(5×10-3molLBu4NPF6inCH3CN)5 P-2Fig.5 CyclicvoltammogramofP-2(5×10-3molLBu4NPF6inCH3CN) 3.P-1、P-2HOMOLUMO2.61eV、3.25eV,,。[1] GermG,LeditzkyG.[J].AdvMater,1:36.[2] YangZ,SokolikI,KaraszFE.[J].Macromolecules,1993,26:1188.[3] ,,,.[J].,1993,24(2):97.[4] YangZ,SokolikI,Kar