| Containing quinoxaline compound is a research focus on the organic electronicdevice materials. In recent years, containing quinoxaline unit compound have beenreported many of organic electronic devices. Synthesise containing quinoxalinylgroup of small molecules and polymers, and study their properties, have greatsignificance for discovery new type of organic solar energy conversion device,organic light emitting device, and battery materials.In this thesis, the benzothiadiazole as a primary material, synthesise of dibromo,dithiophene and di(ethylene dioxythiophene) were substituted acenaphthene-quinoxaline, phenanthrenequinoxaline main derived monomer. And synthesis12typeof alternating conjugated copolymers by Sonogashira reaction, Stille reaction andelectrochemical polymerization.Details are as follows：1. The benzo-thiadiazole as a primary material,5,10–dibromo-2,3,7,8–acenaphthene-quinoxaline(M1) and5,10-dibromo-2,3,7,8–Phenanthrenequinoxaline(M2) were synthesized by nitration, reduction, and condensation reaction. Itsalternating copolymers of poly (2,5-didodecyloxy-3,4-diethynyl–phenylene-alt-2,3,7,8–diacenaphthenequinoxaline)(P1)andpoly (2,5–didodecyloxy-1,4-diethynyl–phenylene–alt-2,3,7,8–diphenanthrenequinoxaline)(P2) wereprepared with2,5–didodecyloxy-1,4-diethynlbenzene by Sonogashira reaction.And these structures of monomers were characterized by FT-IR and1H-NMR. Inthe Uv-Vis absorbance of the monomers and polymers, M1maximum absorptionwavelength appeared at339nm,354nm and317nm,436nm in CHCl3respectively. The maximum absorption wavelength of the monomer M2appearsdouble absorption peaks at304nm,317nm; in long wave appears doubleabsorption peaks at431nm,459nm. The maximum absorption wavelength ofpolymer P1appears at448nm, two absorption peaks appears at305nm and317nm. The PL spectra of monomers shows that maximum emission peaks appearsat480nm and579nm respectively, and the polymer’s maximum emission peaksappears at487nm and478nm respectively. The XRD pattern of polymersobtained by the X-ray diffraction (XRD) showed lower crystallinity. 2.5,10-dibromo–di(acenaphthene/phenanthrene) quinoxaline alternatingcopolymerize with2,5-bis (tributylstannyl) thiophene and2,5-bis(tributylstannyl)3,4-ethylene dioxythiophene respectively by Stille reaction, andstructural characterize for polymer and discussed optical, electrical properties.Poly (bis-acenaphthene quinoxaline-thiophene)(P3), and poly(bis-phenanthrenylquinoxaline-thiophene)(P4) has a blue-shift in trifluoroaceticacid, and poly (bis-acenaphthenequinoxaline-ethylene dioxythiophene)(P5), andpoly (bis-phenanthrenylquinoxaline-ethylene dioxythiophene)(P6) has a redshift in trifluoroacetic acid. They have a poor electrochemical performance, but inthe negative potential (about-1.05V) appears to restore doping， positivepotential (about1.3V) appears oxide doped peak. The PL spectra of polymersshows that maximum emission peaks appears at642nm、630nm、447nm、540nmrespectively. The XRD pattern of polymers obtained by the X-ray diffraction(XRD) showed P3, P5, P6have different degrees of diffraction peaks, but notobvious for related to the spacing layer peaks.3. Benzo-thiadiazole and5,10-dibromo–di (acenaphthene/phenanthrene)quinoxaline as a primary material synthesized5,10-dithiophen-di(acenaphthene/phenanthrene) quinoxaline (M3, M4) and5,10-di-3-octylthiophen–di (acenaphthene/phenanthrene) quinoxaline. Synthesized four type of polymersthe four monomers by the electrochemical polymerization. And these structures ofmonomers were characterized by FT-IR and1H-NMR. For these monomers werediscussed basic properties of UV-visible fluorescence spectroscopy and XRD etc.for UV-visible absorption spectroscopy (UV-Vis) in comparison M3and M5, M5have125nm redshifts in the long wavelength; in comparison M4and M6, M6have224nm redshifts in the long wavelength. The powder X-ray diffractionpattern showed that M3and M4have good crystallinity which can see a strong,sharp spacing layer peaks. Cyclic Voltammograms properties showed that in thefour type of polymers film P7, P8have no electrochemical stability, but P9, P10have. Electrochromic properties shows that P7, P8, P9, P10have absorbtion peaksin1370nm,1250nm,1630nm,1456nm respectively, and as the voltageincreases the absorptiones strengthened. Their transmittance were44%,41%, 45%,28%respectively; polymers switching times were1.2s,1.3s,1.7s,1.5srespectively.4.5,10-dibromo–di (acenaphthene/phenanthrene)quinoxaline as a primary materialsynthesized5,10-diethylenedioxythiophene-di(acenaphthene/phenanthrene)quinoxaline (M7, M8) respectively. Structural characterized and optical studiedfor monomers and they were electrochemical polymerized and discussed electricalproperties for two types of polymeres. Cyclic Voltammograms properties showedP11, P12have electrochemical stability. The electrochromic properties shows thatP11, P12have absorbtion peaks in1254nm,1241nm respectively, and as thevoltage increases the absorption strengthened; Their transmittance were of93%,32%respectively; polymers switching times was1.8s,1.5s respectively. |
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