Precision Synthesis of Various Low‐Bandgap Donor–Acceptor Alternating Conjugated Polymers via Living Suzuki–Miyaura Catalyst‐Transfer Polymerization

Kim, Hwangseok; Lee, Jaeho; Kim, Tae Hyun; Cho, Minyoung; Choi, Tae‐Lim

doi:10.1002/anie.202205828

Cited by 28 publications

(13 citation statements)

References 80 publications

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“…Therefore, boronic acid did not need any protecting group to increase the reaction concentration and directly participated in the polymerization to accelerate this process (Figure c). Moreover, the living Suzuki–Miyaura catalyst-transfer polymerization was used for synthesizing various donor–acceptor alternating conjugated polymers, which exhibited a tunable optical band gap and highest occupied molecular orbital (HOMO) level …”

Section: N-coordinated Boranes and Boronate Esters For Polymer Synthesismentioning

confidence: 99%

“…Moreover, the living Suzuki−Miyaura catalysttransfer polymerization was used for synthesizing various donor−acceptor alternating conjugated polymers, which exhibited a tunable optical band gap and highest occupied molecular orbital (HOMO) level. 57 The reaction rates of various boronate esters were also compared for Suzuki−Miyaura catalyst-transfer polymerization, thereby showing that the length of the N→B dative bond illustrated the origin of the difference in reactivity via density functional theory (DFT) calculations, 25 which might give us enlightenment to affect the performance by constructing the chemical structures.…”

Section: N-coordinated Boronate Esters For Suzuki−miyaura Polymerizationmentioning

confidence: 99%

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N-Coordinated Organoboron in Polymer Synthesis and Material Science

Dong

et al. 2022

ACS Polym. Au

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Organoboron chemistry has been widely explored and developed in synthetic chemistry for over half a century and provides various elegant synthetic protocols in polymer synthesis. Compared with most trivalent bare organoboron compounds, Ncoordinated organoboron shows better performances, such as air and moisture stability. This review summarizes the application of various N-coordinated boranes and boronic acid/esters in polymer synthesis and materials science. We introduce the significance of N-coordinated boranes and boronate esters for controllable polymer synthesis and systematically summarize the structures and properties of polymers containing N-coordinated boronate esters. Furthermore, we highlight the effect of N→B dative bonds on improving the performance of self-healing materials. We hope that, through this review, more researchers will realize the advantages of N-coordinated organoboron and promote the development of this direction in polymer synthesis and materials science.

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Section: N-coordinated Boranes and Boronate Esters For Polymer Synthesismentioning

confidence: 99%

Section: N-coordinated Boronate Esters For Suzuki−miyaura Polymerizationmentioning

confidence: 99%

N-Coordinated Organoboron in Polymer Synthesis and Material Science

Dong

et al. 2022

ACS Polym. Au

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“…In contrast to ROAMP, catalyst-transfer polymerization (CTP) directly provides (hetero)aromatic conjugated polymers with excellent molecular weight control and low dispersity ( Đ ). − Indeed, previous studies from the Yokozawa group have successfully synthesized molecular weight-controlled polyphenylene through living CTP methods. , Hence, CTP could be a promising strategy for the synthesis of length-controlled GNRs. Recently, our group has developed an efficient living Suzuki–Miyaura CTP (SCTP) method for the precise synthesis of various donor/acceptor (D/A) conjugated polymers where use of powerful RuPhos and SPhos Pd G3 precatalysts facilitated external initiation with various aryl iodides including macroinitiators. − Furthermore, the stability and reactivity of the monomers were also tuneable by rational design of boronates, thereby improving SCTP controllability. , As results of both features, the scope of (hetero)arene monomers greatly expanded exceeding that of other conventional catalysts. − Herein, we report the precise synthesis of length-controlled and structurally well-defined armchair GNRs (AGNRs) using SCTP (Figure c). By combining RuPhos Pd G3 and an activated neopentylglycol boronate ((neop)B) monomer, a precursor polymer, poly(2,5-dialkynyl- p -phenylene) (PDAPP), was obtained with excellent molecular weight control and narrow Đ in high yield.…”

Section: Introductionmentioning

confidence: 99%

Living Suzuki–Miyaura Catalyst-Transfer Polymerization for Precision Synthesis of Length-Controlled Armchair Graphene Nanoribbons and Their Block Copolymers

et al. 2023

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The bottom-up synthesis of graphene nanoribbons (GNRs) offers a promising approach for designing atomically precise GNRs with tuneable photophysical properties, but controlling their length remains a challenge. Herein, we report an efficient synthetic protocol for producing length-controlled armchair GNRs (AGNRs) through living Suzuki–Miyaura catalyst-transfer polymerization (SCTP) using RuPhos–Pd catalyst and mild graphitization methods. Initially, SCTP of a dialkynylphenylene monomer was optimized by modifying boronates and halide moieties on the monomers, affording poly(2,5-dialkynyl-p-phenylene) (PDAPP) with controlled molecular weight (M n up to 29.8k) and narrow dispersity (Đ = 1.14–1.39) in excellent yield (>85%). Subsequently, we successfully obtained N = 5 AGNRs by employing a mild alkyne benzannulation reaction on the PDAPP precursor and confirmed their length retention by size-exclusion chromatography. In addition, photophysical characterization revealed that a molar absorptivity was directly proportional to the length of the AGNR, while its highest occupied molecular orbital (HOMO) energy level remained constant within the given AGNR length. Furthermore, we prepared, for the very first time, N = 5 AGNR block copolymers with widely used donor or acceptor-conjugated polymers by taking advantage of the living SCTP. Finally, we achieved the lateral extension of AGNRs from N = 5 to 11 by oxidative cyclodehydrogenation in solution and confirmed their chemical structure and low band gap by various spectroscopic analyses.

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“…17,18 Notably, the selective excitation of growing chains enables a one-pot chain extension reaction to produce all-conjugated block copolymers, a historically challenging class of materials to access. [19][20][21] In this work, we investigate the effects of OEG side chains on reactivity in the photopolymerization, including monomer generation, optical absorption, and surface wettability of the reactivity polymers. We study a suite of OEG-substituted monomers, including linear, branched, and homologated side chains.…”

mentioning

confidence: 99%

Side-chain engineering in hydrophilic n-type π-conjugated polymers for enhanced reactivity

Berl¹,

Sklar²,

Yun³

et al. 2023

Preprint

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Minor changes to side chains in conjugated polymers can have pronounced effects on polymer properties by altering backbone planarity, solubility, and interaction with ions. Here, we report the photocontrolled synthesis of hydrophilic CPs from Grignard monomers and find that switching from alkyl to oligo(ethylene glycol) (OEG) side chains changes their photoreactivity. Specifically, installing hydrophilic side chains on the same monomer core yields higher molecular weight polymers and allows polymerization to proceed with lower-energy red light. Additionally, we discover a side chain decomposition pathway for N-OEG monomers, which are prevalent in CP research. Decomposition can be overcome by adding an extra methylene unit in the side chains without compromising polymer molecular weight or hydrophilicity. Importantly, this polymerization does not require transition metal catalysts and is a promising approach to the preparation of n-type conjugated block copolymers.

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Precision Synthesis of Various Low‐Bandgap Donor–Acceptor Alternating Conjugated Polymers via Living Suzuki–Miyaura Catalyst‐Transfer Polymerization

Cited by 28 publications

References 80 publications

N-Coordinated Organoboron in Polymer Synthesis and Material Science

N-Coordinated Organoboron in Polymer Synthesis and Material Science

Living Suzuki–Miyaura Catalyst-Transfer Polymerization for Precision Synthesis of Length-Controlled Armchair Graphene Nanoribbons and Their Block Copolymers

Side-chain engineering in hydrophilic n-type π-conjugated polymers for enhanced reactivity

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