To branch or not to branch: C–H selectivity of thiophene-based donor–acceptor–donor monomers in direct arylation polycondensation exemplified by PCDTBT

Lombeck, Florian; Marx, Franziska; Strassel, Karen; Kunz, Susanna V.; Lienert, Caroline; Komber, Hartmut; Friend, Richard H.; Sommer, Michael

doi:10.1039/c7py00879a

Cited by 35 publications

(36 citation statements)

References 43 publications

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“…This risk is absent when the brominated monomer in a copolymerization is either a C 6 arene or a thiophene structure which does not have available CH bonds adjacent to the CBr bond . This may explain the high quality of polymers obtained in these instances …”

Section: Adapting Monomer Design To Polymerization Via Ch Activationmentioning

confidence: 99%

CH Activation as a Shortcut to Conjugated Polymer Synthesis

Blaskovits

Leclerc

2018

Macromol. Rapid Commun.

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Direct (hetero)arylation polymerization exploits the palladium-catalyzed activation of aromatic CH bonds for the atom-economical synthesis of conjugated polymers for a wide range of applications. This account outlines how direct arylation methodologies overcome many of the limitations of contemporary polymerization techniques at both the research and production scale, and explains how monomer design and reaction conditions must be tailored to ensure high polymer molecular weight, yield, and structural integrity. Current research aims to improve further this reaction's profile as a sustainable methodology while at the same time making it competitive with the Migita-Stille and Miyaura-Suzuki polymerizations both in scope of accessible structures and synthetic efficiency. This feature article charts the recent developments and future directions of CH activation research as it moves toward becoming at once an industrially feasible, environmentally friendly, and synthetically powerful polymerization technique.

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Section: Adapting Monomer Design To Polymerization Via Ch Activationmentioning

confidence: 99%

CH Activation as a Shortcut to Conjugated Polymer Synthesis

Blaskovits

Leclerc

2018

Macromol. Rapid Commun.

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“…These phenylene and naphthalene polymers are prepared by Suzuki or Stille couplings, but there are some recent examples of dialkoxyphenylene-based polymers successfully synthesized by DAP with high molecular weight [40][41][42][43]. These examples added to the significant advances made in preparing well-defined conjugated polymers via DAP [44][45][46][47][48][49][50][51][52], open the door to produce CPs based on 2,3-dialkoxynaphthalene.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of a 2,3-Dialkoxynaphthalene-Based Conjugated Copolymer via Direct Arylation Polymerization (DAP) for Organic Electronics

et al. 2020

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Poly[(5,5’-(2,3-bis(2-ethylhexyloxy)naphthalene-1,4-diyl)bis(thiophene-2,2′-diyl))-alt-(2,1,3-benzothiadiazole-4,7-diyl)] (PEHONDTBT) was synthesized for the first time and through direct arylation polymerization (DAP) for use as p-donor material in organic solar cells. Optimized reaction protocol leads to a donor-acceptor conjugated polymer in good yield, with less structural defects than its analog obtained from Suzuki polycondensation, and with similar or even higher molecular weight than other previously reported polymers based on the 2,3-dialkoxynaphthalene monomer. The batch-to-batch repeatability of the optimized DAP conditions for the synthesis of PEHONDTBT was proved, showing the robustness of the synthetic strategy. The structure of PEHONDTBT was corroborated by NMR, exhibiting good solubility in common organic solvents, good film-forming ability, and thermal stability. PEHONDTBT film presented an absorption band centered at 498 nm, a band gap of 2.15 eV, and HOMO and LUMO energy levels of −5.31 eV and −3.17 eV, respectively. Theoretical calculations were performed to understand the regioselectivity in the synthesis of PEHONDTBT and to rationalize its optoelectronic properties. Bilayer heterojunction organic photovoltaic devices with PEHONDTBT as the donor layer were fabricated to test their photovoltaic performance, affording low power-conversion efficiency in the preliminary studies.

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“…xylenes, toluene, tetrahydrofuran (THF), dimethylformamide, and dimethylacetamide are energy demanding in terms of synthesis and purification and possess a high level of toxicity. [ 15,16 ]…”

Section: Introductionmentioning

confidence: 99%

Optimization of the Reaction Conditions for Direct Arylation Polymerizations in a Sustainable Solvent

Conelli

Grisorio

Suranna

2020

Macro Chemistry & Physics

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Direct arylation polymerization (DArP) relieves the synthesis of conjugated polymers from the use of hazardous and toxic reagents typical of the traditional protocols. However, the compatibility with environmentally benign, nonhazardous, and low‐cost solvents still represents the critical aspect for projecting DArP as an industrial‐scale method for the preparation of conjugated polymers. In this study, a “green” solvent (i.e., cyclopentyl methyl ether) is implemented for the obtainment of poly(3‐hexylthiophene) by DArP reaction, in order to explore sustainable reaction conditions also regarding the catalytic system and the base quantity, which equally undermine the sustainability of the DArP protocol. Considering the molecular weights as the indicator of precatalyst performance in determined conditions, it is established that the cheapest palladium source (i.e., PdCl2) combined with two equivalents of (o‐anisyl)3P is able to yield the best results in the green ethereal solvent. Furthermore, it is found how, with respect to the common DArP protocols, the quantity of the expensive base (i.e., Cs2CO3) can be reduced in these reaction conditions without compromising molecular weights and regioregularity of the resulting polymer. These optimized reaction conditions can be extended to the copolymerization of other monomer units with satisfactory results in terms of molecular weights.

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To branch or not to branch: C–H selectivity of thiophene-based donor–acceptor–donor monomers in direct arylation polycondensation exemplified by PCDTBT

Abstract: The possibility for unselective C–H activation of a thiophene-based, donor–acceptor–donor monomer during direct arylation polycondensation is investigated.

Cited by 35 publications

References 43 publications

CH Activation as a Shortcut to Conjugated Polymer Synthesis

CH Activation as a Shortcut to Conjugated Polymer Synthesis

Synthesis and Characterization of a 2,3-Dialkoxynaphthalene-Based Conjugated Copolymer via Direct Arylation Polymerization (DAP) for Organic Electronics

Optimization of the Reaction Conditions for Direct Arylation Polymerizations in a Sustainable Solvent

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