Synthesis of conjugated polymers using aryl-bromides <i>via</i> Cu-catalyzed direct arylation polymerization (Cu-DArP)

Ye, Liwei; Pankow, Robert M.; Schmitt, Alexander; Thompson, Barry C.

doi:10.1039/c9py01478k

Cited by 17 publications

(36 citation statements)

References 37 publications

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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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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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“…[49] Subsequently, the same group reported alternate reaction conditions in 2019 whereby even di-bromofluorene could be used as the monomer (Scheme 7b). [50] Under optimised conditions, polymer A7b with an M n of 17 kg/mol and moderate yield of 55% could be obtained. The same reactions conditions could be applied to other monomers including thiophene and TPD.…”

Section: Polymers Containing the Fluorene Moietymentioning

confidence: 99%

“…Copyright 2011 American Chemical Society (b) Preparation of fluorene-bi-tetrafluorobenzene co-polymer A7b by copper catalysed DArP. [50] Scheme 8. Semi random P3HT-BTD prepared by (a) DArP, (b) Stille polymerisation.…”

Section: Polymers Containing the Benzothiadiazole (Btd) Moietymentioning

confidence: 99%

“…Another option is to develop recyclable heterogeneous catalysts systems or use more low-cost metals (e. g. iron, nickel and copper) complexes. [50,82] To improve efficiency and selectivity of direct cross-coupling between co-monomers, bimetallic catalytic systems may also be a viable way forward with each metal centre playing a different role in substrate activation and CÀ C bond formation. In addition, the role of ligands cannot be overlooked as well, so further refinement into the design of phosphine, NHC ligands and even tetradentate C 2 -symmetric ligand (salens) may be useful to improve polymerization yield, MW and regionselectivity.…”

Section: Perspectives and Conclusionmentioning

confidence: 99%

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Synthesis of Conjugated Polymers via Transition Metal Catalysed C−H Bond Activation

Chua

Png

Zhu

et al. 2021

Chemistry An Asian Journal

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Transition metal catalysed CÀ H bond activation chemistry has emerged as an exciting and promising approach in organic synthesis. This allows us to synthesize a wider range of functional molecules and conjugated polymers in a more convenient and more atom economical way. The formation of CÀ C bonds in the construction of piconjugated systems, particularly for conjugated polymers, has benefited much from the advances in CÀ H bond activation chemistry. Compared to conventional transitionmetal catalysed cross-coupling polymerization such as Suzuki and Stille cross-coupling, pre-functionalization of aromatic monomers, such as halogenation, borylation and stannylation, is no longer required for direct arylation polymerization (DArP), which involve CÀ H/CÀ X cross-coupling, and oxidative direct arylation polymerization (Ox-DArP), which involves CÀ H/CÀ H cross-coupling protocols driven by the activation of monomers' C(sp 2 )À H bonds. Furthermore, poly(annulation) via CÀ H bond activation chemistry leads to the formation of unique pi-conjugated moieties as part of the polymeric backbone. This review thus summarises advances to date in the synthesis of conjugated polymers utilizing transition metal catalysed CÀ H bond activation chemistry. A variety of conjugated polymers via DArP including poly(thiophene), thieno [3,4-c]pyrrole-4,6-dione)-containing, fluorenyl-containing, benzothiadiazole-containing and diketopyrrolopyrrolecontaining copolymers, were summarized. Conjugated polymers obtained through Ox-DArP were outlined and compared. Furthermore, poly(annulation) using transition metal catalysed CÀ H bond activation chemistry was also reviewed. In the last part of this review, difficulties and perspective to make use of transition metal catalysed CÀ H activation polymerization to prepare conjugated polymers were discussed and commented.

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“…Thompson and colleagues published a series of studies on copper catalyzed DArP to synthesize D-A copolymers. [107][108][109][110] The first copper catalyzed DArP for D-A copolymer synthesis was reported in 2018 by Thompson. Thieno [3,4-c]pyrrole-4,6-dione (TPD)-containing D-A copolymers were prepared with the catalyst loading of 50 mol% and the molecular weights of B 4k to B10 kg mol À1 (Scheme 12b, top).…”

Section: Energy-efficient Conditions In Atom-economical Synthesesmentioning

confidence: 99%

Advances in applying C–H functionalization and naturally sourced building blocks in organic semiconductor synthesis

Xing

Luscombe

2021

J. Mater. Chem. C

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Synthesis of conjugated polymers using aryl-bromides via Cu-catalyzed direct arylation polymerization (Cu-DArP)

Abstract: The first report on direct arylation polymerization with copper catalysts and aryl-bromide monomers expands the sustainability and practicality of DArP.

Cited by 17 publications

References 37 publications

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

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

Synthesis of Conjugated Polymers via Transition Metal Catalysed C−H Bond Activation

Advances in applying C–H functionalization and naturally sourced building blocks in organic semiconductor synthesis

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