Direct heteroarylation of β-protected dithienosilole and dithienogermole monomers with thieno[3,4-c]pyrrole-4,6-dione and furo[3,4-c]pyrrole-4,6-dione

Mercier, Lauren G.; Aïch, Badrou Réda; Najari, Ahmed; Beaupré, Serge; Berrouard, Philippe; Proñ, Agnieszka; Robitaille, Amélie; Tao, Ye; Leclerc, Mario

doi:10.1039/c3py21138j

Cited by 47 publications

(47 citation statements)

References 43 publications

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“…[26][27][28][29]34 Obviously, as all lowintensity signals of the 1 H NMR spectrum were successfully assigned, the presence of main chain defects can be excluded indirectly as those are expected to give chemical shifts significantly different from backbone and end group signals. However, a direct proof of the absence of homocouplings is additionally given by a low-MW model compound T2-NDI-NDI-T2 and by the copolymer PNDIT4, which mimic the chemical shifts of such species.…”

Section: Scheme 1 Synthesis Of Pndit2 Via Direct Arylation Polycondementioning

confidence: 99%

Defect-free Naphthalene Diimide Bithiophene Copolymers with Controlled Molar Mass and High Performance via Direct Arylation Polycondensation

et al. 2015

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A highly efficient, simple, and environmentally friendly protocol for the synthesis of an alternating naphthalene diimide bithiophene copolymer (PNDIT2) via direct arylation polycondensation (DAP) is presented. High molecular weight (MW) PNDIT2 can be obtained in quantitative yield using aromatic solvents. Most critical is the suppression of two major termination reactions of NDIBr end groups: nucleophilic substitution and solvent end-capping by aromatic solvents via C-H activation. In situ solvent end-capping can be used to control MW by varying monomer concentration, whereby end-capping is efficient and MW is low for low concentration and vice versa. Reducing C-H reactivity of the solvent at optimized conditions further increases MW. Chain perfection of PNDIT2 is demonstrated in detail by NMR spectroscopy, which reveals PNDIT2 chains to be fully linear and alternating. This is further confirmed by investigating the optical and thermal properties as a function of MW, which saturate at Mn ≈ 20 kDa, in agreement with controls made by Stille coupling. Field-effect transistor (FET) electron mobilities μsat up to 3 cm(2)/(V·s) are measured using off-center spin-coating, with FET devices made from DAP PNDIT2 exhibiting better reproducibility compared to Stille controls.

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Section: Scheme 1 Synthesis Of Pndit2 Via Direct Arylation Polycondementioning

confidence: 99%

Defect-free Naphthalene Diimide Bithiophene Copolymers with Controlled Molar Mass and High Performance via Direct Arylation Polycondensation

et al. 2015

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“…Thiophenes can also be fused to other aromatic cores, such as those shown in Figure (benzodithiophene, cyclopentadithiophene, etc.) . These units differ from thiophene‐flanked units in that they do not possess C γ H bonds.…”

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

confidence: 99%

“…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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“…Currently, in the literature describing synthesis of conjugated polymers via DArP two distinct sets of reaction conditions could be identified: the so‐called Fagnou conditions and the so‐called Ozawa conditions (Table ). The Ozawa conditions have been reported for the first time by Ozawa et al for the synthesis of P3HT in 2010 and since then these conditions have been adopted with or without modifications by many research groups for the synthesis of a variety of conjugated polymers . The Ozawa conditions include palladium‐based Herrmann–Beller catalyst, usually with trianisylphosphine as a ligand, THF or toluene as a solvent, Cs 2 CO 3 as a base with or without pivalic acid as a proton shuttle.…”

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.

190

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 heteroarylation of β-protected dithienosilole and dithienogermole monomers with thieno[3,4-c]pyrrole-4,6-dione and furo[3,4-c]pyrrole-4,6-dione

Cited by 47 publications

References 43 publications

Defect-free Naphthalene Diimide Bithiophene Copolymers with Controlled Molar Mass and High Performance via Direct Arylation Polycondensation

Defect-free Naphthalene Diimide Bithiophene Copolymers with Controlled Molar Mass and High Performance via Direct Arylation Polycondensation

CH Activation as a Shortcut to Conjugated Polymer Synthesis

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

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