Single step reductive polymerization of functional 3,4-propylenedioxythiophenes via direct C–H arylation catalyzed by palladium acetate

Kumar, Anshu; Kumar, Anil

doi:10.1039/b9py00265k

Cited by 66 publications

(41 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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%

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.

193

224

View full text Add to dashboard Cite

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.

show abstract

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.

193

224

View full text Add to dashboard Cite

show abstract

“…21 Usually EDOT-chalcogenadiazole copolymers were synthesized through electrochemical polymerization. 21 Usually EDOT-chalcogenadiazole copolymers were synthesized through electrochemical polymerization.…”

Section: Polymer Synthesismentioning

confidence: 99%

Third-order nonlinear optical properties of 3,4-ethylenedioxythiophene copolymers with chalcogenadiazole acceptors

et al. 2015

View full text Add to dashboard Cite

Two 3,4-ethylenedioxythiophene (EDOT) based low band gap donor-acceptor (D-A)conjugated copolymers were designed and synthesized via direct arylation, in which the HOMO-LUMO gaps were fine-tuned by the regular insertion of electron deficient units, 2,1,3-benzothiadiazole (BTZ) and 2,1,3-benzoselenadiazole (BTSe), respectively. Structural characterization was performed by FT-IR, 1 H NMR and XPS. In order to investigate the variation in energy band structure of the copolymers, quantum-chemical calculation using density functional theory was carried out. The alternating insertion of chalcogenadiazole unit in the PEDOT (poly(3,4-ethylenedioxythiophene)) lowers the HOMO and LUMO energy levels. As a result, the polymers with lower band gap compared to that of the homopolymer, PEDOT was obtained. Optical and electrochemical results confirmed that BTSe is marginally superior to BTZ in EDOT based alternate donor-acceptor copolymers. Present experimental results correlate with HSE06 level theoretical calculations than those with B3LYP level. Zscan experiments reveal that the copolymers exhibit strong nonlinear absorption coefficient and nonlinear refraction coefficient of the order 10 -10 esu and the third-order nonlinear susceptibility is of the order of 10 -11 esu. These findings indicated that the EDOTchalcogenadiazole copolymers can be developed into excellent third-order nonlinear optical material.

show abstract

“…This may have resulted in low‐molecular‐weight polymers. Variations of these conditions have later been used to synthesize dioxythiophene‐based polymers . A remarkably different procedure has been developed by Ozawa and coworkers for the synthesis of P3HT.…”

Section: Introductionmentioning

confidence: 99%

“…Variations of these conditions have later been used to synthesize dioxythiophene-based polymers. 16,17 A remarkably different procedure has been developed by Ozawa and coworkers 14,18 for the synthesis of P3HT. The optimized conditions include Herrmann's catalyst, cesium carbonate, tris(o-(N,N-dimethyl) anilyl)phosphine, and superheated tetrahydrofuran as a solvent.…”

mentioning

confidence: 99%

Optimization of direct arylation polymerization conditions for the synthesis of poly(3‐hexylthiophene)

Rudenko

Wiley

Tannaci

et al. 2013

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

120

View full text Add to dashboard Cite

Direct arylation polymerization (DArP) is an emerging alternative to Stille and Suzuki polymerizations. This method is attractive as it allows preparation of high‐molecular‐weight conjugated polymers in good yield without the need to metallate monomers. Despite this promise, for poly(3‐hexylthiophene) (P3HT) and related polymers that have β‐protons on the thiophene ring, DArP is known to produce β‐defects, which make the polymer properties different from polymers produced by traditional methods. Here, we demonstrate that DArP conditions based on simple, inexpensive, and bench‐stable reagents can be tuned to limit the amount of defects and produce P3HT with properties remarkably similar to Stille P3HT. Specifically, lowering the reaction temperature, lowering the amount of catalyst, and using a bulkier carboxylate ligand is critical. Optimized conditions include reacting 2‐bromo‐3‐hexylthiophene with 0.25 mol % of Pd(OAc)2, 1.5 equivalents of K2CO3, and 0.3 equivalents of neodecanoic acid in N,N‐dimethylacetamide at 70 °C and give DArP P3HT with ∼60% yield, regioregularity of 93.5%, molecular weight of 20 kDa, polydispersity of 2.8, and melting point of 217 °C, providing a very close match to Stille P3HT, which is obtained with 70–80% yield, 91–94% regioregularity, molecular weight of 15–25 kDa, polydispersity of 2.5–2.8, and melting point of 214–221 °C. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2660–2668

show abstract

Single step reductive polymerization of functional 3,4-propylenedioxythiophenes via direct C–H arylation catalyzed by palladium acetate

Abstract: In this Communication we report a single step reductive polymerization of ProDOT derivatives which is compatible with functional side chains and is amenable for scale-up.

Cited by 66 publications

References 27 publications

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

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

Third-order nonlinear optical properties of 3,4-ethylenedioxythiophene copolymers with chalcogenadiazole acceptors

Optimization of direct arylation polymerization conditions for the synthesis of poly(3‐hexylthiophene)

Contact Info

Product

Resources

About