Regiodefined substituted poly(2,5‐thienylene)s

Gallazzi, M. C.; Castellani, L.; Marín, Romina; Zerbi, G.

doi:10.1002/pola.1993.080311322

Cited by 78 publications

(62 citation statements)

References 72 publications

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“…4 Although the synthesis of alkyl and di-alkoxy substituted polythiophenes has been well established, 5,6 the synthesis of monoalkoxy substituted polythiophenes still remains a problem due to the low molecular weight and poor solubility. [7][8][9][10][11][12][13][14] This paper reports the synthesis and optical properties of three poly(3-alkoxythiophene) derivatives with moderately high molecular weights, which exhibit good solubility and film-forming ability. The introduction of a branched side chain in the monomer increased molecular weight of the polymer.…”

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confidence: 99%

Synthesis and Molecular Weight Dependent Optical Properties of Mono-Alkoxy Substituted Polythiophenes

Zhang

Fujiki

2001

Polym J

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ABSTRACT:Poly(3-alkoxythiophene)s with moderately high molecular weights, which exhibit good solubility and film-forming ability, were successfully synthesized by the nickel (0) coupling reaction in good yields. The introduction of a branched side chain resulted in a molecular weight higher than that of the straight one. Broad photoluminescence (PL), ranging from 579 to 684 nm, was readily obtained by choosing the appropriate molecular weight sample of a mother polymer. This may provide a new method for evaluating organic luminescent materials.KEY WORDS Poly(3-alkoxythiophene) / Nickel Catalyst / Molecular Weight / Optical Properties / π-Conjugating polythiophenes have been considered promising candidates for polymer light-emitting diodes (LEDs), due to the tunability of emission colors, processability, and thermal and chemical stabilities. 1 Emission color closely depends on the extent of the effective conjugation along the backbone, which is mainly controlled by tailoring the structures of the main chain and side chain. 2, 3 Poly(alkoxythiophene)s are known to be useful as hole injection layers to improve the charge transport ability of LEDs, due to higher charge carrier mobility, lower oxidation potential, and better stability in the oxidized state, compared to alkyl substituted polythiophenes. 4 Although the synthesis of alkyl and di-alkoxy substituted polythiophenes has been well established, 5, 6 the synthesis of monoalkoxy substituted polythiophenes still remains a problem due to the low molecular weight and poor solubility. [7][8][9][10][11][12][13][14] This paper reports the synthesis and optical properties of three poly(3-alkoxythiophene) derivatives with moderately high molecular weights, which exhibit good solubility and film-forming ability. The introduction of a branched side chain in the monomer increased molecular weight of the polymer. These results may lead to a facile and inexpensive method for providing variable emission color by choosing the appropriate molecular weight samples of a single mother polymer. EXPERIMENTAL MeasurementsMolecular weights were evaluated by size exclusion chromatography (SEC) on a Shodex KF806 M column (eluent THF, 30 • C) in a Shimadzu liquid chromatography instrument equipped with a photodiode array detector based on the calibration using polystyrene stan- † To whom correspondence should be addressed.dards. Ultraviolet-visible (UV-vis) spectra (room temperature; 21 • C) were recorded on a JASCO V-570 spectrometer. Fluorescence spectra (room temperature; 21 • C) were recorded on a Hitachi F-850 spectrophotometer. NMR spectra were recorded on a Varian Unity 300 spectrometer relative to the TMS internal standard in chloroform-d. Materials3-Methoxythiophene was purchased from Aldrich Chemical Co. (R)-(−)-2-Octanol (≥ 99% e.e. (enantiomeric excess)) was purchased from AZmax Co., Japan. They were used without further purification. Monomer Synthesis3-Alkoxy substituted thiophenes were prepared by transetherification reaction between 3-methoxythiophene and corresponding pr...

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Synthesis and Molecular Weight Dependent Optical Properties of Mono-Alkoxy Substituted Polythiophenes

Zhang

Fujiki

2001

Polym J

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“…The use of 4, 4''-dialkoxy-3-substituted terthiophenes as a precursor for developing novel substituted poly(thiophene)s provides reduced steric interactions between polymer backbone and substituent, allows better control of polymer regiochemistry, and the alkoxy side chains activate the monomer for polymerization and ensure better polymer processability. 21,22 We have been exploring successfully the polymerization of functionalized dialkoxyterthiophene monomers in order to avoid these problems. 22,23 Incorporation of the spiropyran moiety into a dialkoxyterthiophene monomer appeared to provide a good opportunity to investigate the potential for electrochemical control of photoresponsive functionality in a conducting polymer system.…”

Section: Introductionmentioning

confidence: 99%

A Multiswitchable Poly(terthiophene) Bearing a Spiropyran Functionality: Understanding Photo- and Electrochemical Control

et al. 2011

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An electroactive nitrospiropyran-substituted polyterthiophene, 2-(3,3′′-dimethylindoline-6′-nitrobenzospiropyranyl)ethyl 4,4′′-didecyloxy-2,2′:5′,2′′-terthiophene-3′-acetate, has been synthesized for the first time. The spiropyran, incorporated into the polymer backbone by covalent attachment to the alkoxyterthiophene monomer units, leads to multiple coloured states as a result of both electrochemical isomerization of the spiropyran moiety to merocyanine forms as well as electrochemical oxidation of the polyterthiophene backbone and the merocyanine substituents. While electrochemical polymerization of the terthiophene monomer could occurs without the apparent oxidation of the spiropyran, the subsequent electrochemistry is complex and clearly involves this substituent. In order to understand this complex behaviour, the first detailed electrochemical study of the oxidation of the precursor spiropyran, 1-(2-hydroxyethyl)-3,3-dimethylindoline-6'-nitrobenzospiropyran, was undertaken, showing that, in solution, an irreversible electrochemical oxidation of the spiropyran occurs leading to reversible redox behaviour of at least two merocyanine isomers. With these insights, an extensive electrochemical and spectroelectrochemical study of the nitrospiropyran-substituted polyterthiophene films reveals an initial irreversible electrochemical oxidative ring opening of the spiropyran to oxidized merocyanine. Subsequent reduction and cyclic voltammetry of the resulting nitromerocyanine-substituted polyterthiophene film gives rise to the formation of both merocyanine π-dimers or oligomers and π-radical cation dimers, between polymer chains. Although merocyanine formation is not electrochemically reversible, the spiropyran can be photochemically regenerated, at least in part, through irradiation with visible light. SEM and AFM images support the conclusion that the bulky spiropyran substituent is electrochemically isomerizes to the planar merocyanine moiety affording a smoother polymer film. The conductivity of the freestanding polymer film was found to be 0.4 S cm -1 .3

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“…and more regioregular polymers with correspondingly high conductivity. 11 In order to explore the processability of polymers with intramolecular charge transfer interactions, copolymers of the indanedione-substituted terthiophene and a dihexylterthiophene were synthesized. The electrochemically polymerized homopolymers of the indanedione terthiophenes showed promise for expanding the range of light absorbance in polythiophenes, but they suffer from a lack of processability.…”

Section: Introductionmentioning

confidence: 99%

Indanedione-Substituted Poly(terthiophene)s: Processable Conducting Polymers with Intramolecular Charge Transfer Interactions

et al. 2010

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Officer, D. L. (2010). Indanedione-substituted poly(terthiophene)s: Processable conducting polymers with intramolecular charge transfer interactions. Macromolecules, 43 (8), 3817-3827. Indanedione-substituted poly(terthiophene)s: Processable conducting polymers with intramolecular charge transfer interactions AbstractThe electrochemical and chemical syntheses of poly(terthiophene)s bearing an indanedione pendant group and displaying intramolecular charge transfer interactions have been achieved. The nature of the charge transfer interaction is characterized through DFT calculations and experimental studies, including resonance Raman spectroscopy and absorption and emission data through a Lippert-Mataga analysis. It is found that the low-energy transition present in the indanedione-bearing monomer species has considerable charge transfer character with a dipole change of II D. Decomposition of the indanedione group occurred during hydrazine reduction after chemical polymerization. A soluble, low molecular weight indanedione-substituted polymer (weight average 4500 Da) was nonetheless obtained following the use of a milder reducing agent, triethanolamine. To the best of our knowledge, this is the first example of the use of triethanolamine for the reduction of an oxidized polythiophene, providing a milder and safer alternative to hydrazine. In an attempt to produce higher molecular weight processable polymers with intramolecular charge transfer interactions, a copolymer of the indanedione-substituted terthiophene and a dihexylterthiophene was synthesized. The electronic conjugation of the produced polymers was characterized by Raman frequency dispersion experiments and show dispersion rate parameters similar to those observed for other substituted polythiophenes. ABSTRACT: The electrochemical and chemical syntheses of poly(terthiophene)s bearing an indanedione pendant group and displaying intramolecular charge transfer interactions have been achieved. The nature of the charge transfer interaction is characterized through DFT calculations and experimental studies, including resonance Raman spectroscopy and absorption and emission data through a Lippert-Mataga analysis. It is found that the low-energy transition present in the indanedione-bearing monomer species has considerable charge transfer character with a dipole change of 11 D. Decomposition of the indanedione group occurred during hydrazine reduction after chemical polymerization. A soluble, low molecular weight indanedionesubstituted polymer (weight average 4500 Da) was nonetheless obtained following the use of a milder reducing agent, triethanolamine. To the best of our knowledge, this is the first example of the use of triethanolamine for the reduction of an oxidized polythiophene, providing a milder and safer alternative to hydrazine. In an attempt to produce higher molecular weight processable polymers with intramolecular charge transfer interactions, a copolymer of the indanedione-substituted terthiophene and a dihexylterthiophene was synthesized. The ...

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Regiodefined substituted poly(2,5‐thienylene)s

Cited by 78 publications

References 72 publications

Synthesis and Molecular Weight Dependent Optical Properties of Mono-Alkoxy Substituted Polythiophenes

Synthesis and Molecular Weight Dependent Optical Properties of Mono-Alkoxy Substituted Polythiophenes

A Multiswitchable Poly(terthiophene) Bearing a Spiropyran Functionality: Understanding Photo- and Electrochemical Control

Indanedione-Substituted Poly(terthiophene)s: Processable Conducting Polymers with Intramolecular Charge Transfer Interactions

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