Direct (Hetero)arylation Polymerization: An Effective Route to 3,4-Propylenedioxythiophene-Based Polymers with Low Residual Metal Content

Estrada, Leandro A.; Deininger, James J.; Kamenov, George D.; Reynolds, John R.

doi:10.1021/mz4003886

Cited by 133 publications

(123 citation statements)

References 47 publications

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“…[19,20] Incorporation of a biEDOT unit causes a larger increase in conductivity than a single EDOT unit, even though the overall amount of EDOT in the repeat unit (50%) remains constant. [30][31][32] The Seebeck coefficients for all of these polymers in their oxidatively doped states are relatively low and positive as expected for a good conductor, similar to PEDOT, [5,33,34] with P 2 E having the highest value of 35 µV K −1 at room temperature. This is expected as soluble dioxythiophene based polymers are typically disordered [10,24,25] and other properties of these materials (e.g., λ max or electrochromic contrast) do not show molecular weight dependencies above a certain point, which is unique for each polymer (≈9 kDa as measured by GPC versus polystyrene for PProDOT).…”

Section: Doping Of Xdot Polymers Using Ni(tfd)supporting

confidence: 54%

Conductive, Solution‐Processed Dioxythiophene Copolymers for Thermoelectric and Transparent Electrode Applications

Ponder

Menon

Dasari

et al. 2019

Advanced Energy Materials

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Conjugated polymers with high electrical conductivities are attractive for applications in capacitors, biosensors, organic thermoelectrics, and transparent electrodes. Here, a series of solution processable dioxythiophene copolymers based on 3,4‐propylenedioxythiophene (ProDOT) and 3,4‐ethylenedioxythiophene (EDOT) is investigated as thermoelectric and transparent electrode materials. Through structural manipulation of the polymer repeat unit, the conductivity of the polymers upon oxidative solution doping is tuned from 1 × 10−3 to 3 S cm−1, with a polymer consisting of a solubilizing alkylated ProDOT unit and an electron‐rich biEDOT unit (referred to as PE2) showing the highest electrical conductivity. Optimization of the film casting method and screening of dopants result in AgPF6‐doped PE2 achieving a high electrical conductivity of over 250 S cm−1 and a thermoelectric power factor of 7 μW m−1 K−2. Oxidized spray cast films of PE2 are also assessed as a transparent electrode material for use with another electrochromic polymer. This bilayer shows reversible electrochemical switching from a colored charge‐neutral state to a highly transmissive color‐neutral, oxidized state. These results demonstrate that dioxythiophene‐based copolymers are a promising class of materials, with ProDOT–biEDOT serving as a soluble analog to the well‐studied PEDOT as a p‐type thermoelectric and electrode material.

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Section: Doping Of Xdot Polymers Using Ni(tfd)supporting

confidence: 54%

Conductive, Solution‐Processed Dioxythiophene Copolymers for Thermoelectric and Transparent Electrode Applications

Ponder

Menon

Dasari

et al. 2019

Advanced Energy Materials

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“…The Fagnou conditions have been developed by Fagnou et al for the synthesis of small molecules via direct arylation in 2006 and then later adopted for the synthesis of conjugated polymers with little or no modifications . The conditions include rather simple, inexpensive, and bench‐stable reagents.…”

Section: Structural Defects In Darp Polymersmentioning

confidence: 99%

“…Towards this end, Reynolds et al reported the synthesis of propylenedioxythiophene (ProDOT) containing copolymers via DArP as well as quantification of residual metal defects of the resulting polymers by ICP‐MS (Scheme ) . It has been shown that the element content for DArP polymer (Fagnou conditions) is less than 20 ppm for both palladium and phosphorus, whereas, the same polymer prepared via GRIM contained 1636 ppm of Mg and 926 ppm of Ni and the same polymer made by oxidative coupling with FeCl 3 showed 1112 ppm of Fe.…”

Section: Structural Defects In Darp Polymersmentioning

confidence: 99%

Optimization of direct arylation polymerization (DArP) through the identification and control of defects in polymer structure

Rudenko

Thompson

2014

J. Polym. Sci. Part A: Polym. Chem.

194

224

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As a newly emerged protocol for the synthesis of conjugated polymers, direct arylation polymerization (DArP) is an environmentally friendly and cost-effective alternative to traditional methods of polymerization. DArP efficiently yields conjugated polymers with high yield and high molecular weight. However, DArP is also known to produce defects in polymer chemical structure. Together with molecular weight and polydispersity, these defects are considered to be important parameters of polymer structure and they have a strong impact on optical, electronic and thermal properties of conjugated polymers. The four major classes of conjugated polymer defects inherent for DArP have been identified: homocoupling regiodefects, branching defects, end group defects, and residual metal defects. To have a precise control over the polymer properties, it is important to understand what causes the defects to form during the polymerization process and be able to control their content. Here within the scope of current literature, we discuss in detail the definition and origin of all these defects, their influence on polymer properties and effective means to control the defects through fine tuning of the DArP reaction parameters.

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“…Direct arylation polycondensation between dibrominated DPP monomers and EDOT was investigated because the high reactivity of its CH bond makes it an ideal candidate for direct arylation reactions . In addition, EDOT is expected to serve as a strong electron–donor unit in the polymers.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of conjugated polymers possessing diketopyrrolopyrrole units bearing phenyl, pyridyl, and thiazolyl groups by direct arylation polycondensation: Effects of aromatic groups in DPP on physical properties

Kuwabara

Takase

Yasuda

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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Conjugated polymers containing phenyl-, pyridyl-, and thiazolyl-flanked diketopyrrolopyrrole (DPP) were synthesized by direct arylation polycondensation of 3,4-ethylenedioxythiophene derivatives and dibrominated DPP-based monomers, in order to probe the effects of the aromatic groups in the DPP units on the absorption property, energy level, and crystallinity. A polymer possessing thiazolyl-flanked DPP units was found to display long-wavelength absorption properties and higher crystallinity than the polymers bearing phenyl-and pyridyl-flanked DPP units. These features of the thiazolyl-based polymer were afforded by its coplanar structure of the main chain. The synthesized polymers showed semiconducting properties in organic field effect transistors and organic photovoltaics. Direct arylation polycondensation is an efficient synthetic method that affords a series of DPP-based polymers in a simple fashion and, thus, helping in a comprehensive understanding on the relationship between the aromatic groups in DPP units and their physical properties.

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Direct (Hetero)arylation Polymerization: An Effective Route to 3,4-Propylenedioxythiophene-Based Polymers with Low Residual Metal Content

Cited by 133 publications

References 47 publications

Conductive, Solution‐Processed Dioxythiophene Copolymers for Thermoelectric and Transparent Electrode Applications

Conductive, Solution‐Processed Dioxythiophene Copolymers for Thermoelectric and Transparent Electrode Applications

Optimization of direct arylation polymerization (DArP) through the identification and control of defects in polymer structure

Synthesis of conjugated polymers possessing diketopyrrolopyrrole units bearing phenyl, pyridyl, and thiazolyl groups by direct arylation polycondensation: Effects of aromatic groups in DPP on physical properties

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