New Diketopyrrolopyrrole(DPP)-Based Conjugated Polymers Prepared upon Palladium Catalyzed Polymerization and Electropolymerization Reactions

Zhu, Yu (2006). New Diketopyrrolopyrrole(DPP)-Based Conjugated Polymers Prepared upon Palladium Catalyzed Polymerization and Electropolymerization Reactions. PhD thesis, Universität zu Köln. Open Access

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Abstract

Synthesis and characteristic properties of new conjugated polymers and polyelectrolytes containing DPP-units in the main chain are described. The polymers are synthesized upon palladium-catalyzed Suzuki, Stille and Buchwald-Hartwig polycondensation and electropolymerization. Characteristic properties such as molecular weight, structure, optical and electrooptical properties of the polymers are studied using gel permeation chromatography, spectroscopic methods (UV/vis, Fluorescence, NMR spectroscopy), cyclic voltammetry and spectroelectrochemical characterization. Using the Suzuki, Stille and Buchwald-Hartwig coupling, conjugated polymers are synthesized from dibromo-DPP or the boronic ester of DPP and derivatives of the carbazole (CBZ), triphenylamine (TPA), benzothiadiazole (BTZ), thiophene (TH), bithiophene (BTH), 3,4-ethylenedioxythiophene (EDOT), pyrene (PYRE) or N,N'-diphenyl-1,4-phenylene diamine (PDA). The molecular weights of the resulting polymers are between 4.3 and 16.5 kDa. The polymers are soluble in solvents such as toluene, chloroform or THF forming red to purple solutions with strong photoluminescence. Compared with the DPP monomer, the optical properties of the polymers are bathochromically shifted due to the increase of the conjugated system. Polymers in solution exhibit absorption maxima between 506 and 560 nm, and fluorescence maxima between 585 and 635 nm. The polymer P-DPP-TPA exhibits a photoluminescence quantum yield of 85 %, which is the highest value reported for DPP containing conjugated polymers so far. Polymers of DPP and BTH, PDA and PYRE exhibit reversible electrochromic properties upon electrochemical oxidation and reduction. The abrupt colour changes from purple to dark blue to black-green are observed. Furthermore, a series of electropolymerizable DPP containing monomer have been successfully prepared using Suzuki, Stille or Buchwald-Hartwig coupling. The in-situ formed polymer films are robust and insoluble in common solvents. They exhibit a very good stability during oxidation reduction cycles together with electrochromic properties. The polymer films are useful as active materials in electrochromic devices showing colour changes from blue to transparent, brown-red to olive-green, purple-red to brown-red, and colourless to green. Conjugated polyelectrolytes were synthesized from bis-bromohexyl-DPP or bis-sulfonylbutyl-DPP using Suzuki and Buchwald-Hartwig coupling. The resulting cationic and anionic polyelectrolytes are readily soluble in water and polar organic solvents such as methanol and DMSO. The polymers are non-luminescent in water, but exhibit photoluminescence quantum yields between 6.2 % and 49 % in DMSO.

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Thesis (PhD thesis)

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Ziel dieser Arbeit war die Herstellung und die Charakterisierung von konjugierten Polymeren mit DPP-Einheiten in der Hauptkette. Die Polymere wurden mit Hilfe der Suzuki, Stille und Buchwald-Hartwig Kupplung so wie durch Elektropolymerisation hergestellt. Die Eigenschaften der resultierenden Polymere (Molekulargewicht, UV/vis, Fluoreszenz, NMR Spektroskopie, Zyklovoltammetrische Untersuchungen und spektroelektrochemische Charakterisierung) wurden untersucht. Mit Hilfe der Suzuki, Stille und Buchwald-Hartwig Kupplung, wurden Dibromo-DPP oder Diboronester-DPP mit Carbazol (CBZ), Triphenylamin (TPA), Benzothiadiazol (BTZ), Thiophen (TH), Bithiophen (BTH), 3,4-Ethylenedioxythiophen (EDOT), Pyrene (PYRE) oder N,N'-diphenyl-1,4-phenylene diamin (PDA) gekupplet. Die Molekulargewichte der erhaltenen Polymere liegen zwischen 4.3 und 16.5 kDa. Die Polymeren sind in gängigen Lösemitteln wie Toluol, Chloroform, Dichlormethan oder THF gut löslich. Dabei bilderen sie stark fluoreszierende Lösungen. Die Absorptionsmaxima liegen zwischen 506 und 560 nm, die Fluoreszenz maxima zwischen 585 und 635 nm. Weiterhin wurden DPP-Polymere durch Elektropolymerisation herstellt. Die Polymere sind unter Farbwechsel Oxidationsbeständig. Konjugierte Polyelektrolyte wurde mit Hilfe der Suzuki und Buchwald-Hartwig Kupplungs hergestellt. Die Polymeren sind löslich in Wasser, DMSO und Methanol.

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