Catalyst-transfer system in stoichiometry-independent AA+BB-type Migita–Kosugi–Stille coupling polycondensation using ester-functionalized dibromo monomer

Terayama, Kosuke; Liu, Chuan-Wen; Higashihara, Tomoya

doi:10.1038/s41428-021-00571-2

Cited by 9 publications

(13 citation statements)

References 29 publications

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“…The proposed reaction mechanism of the model reaction is summarized in Figure S3 of the Supporting Information. These findings are consistent with the trends observed in the nonstoichiometric polycondensation via the Suzuki-Miyaura or Migita-Kosugi-Stille coupling [2][3][4][5][6][7][8][9] and nonstoichiometric polyaddition via Co-catalyzed hydroarylation. [35] Another control experiment was conducted under conventional Pd-catalyzed direct arylation conditions, which have been optimized for polycondensation of 1 with 2,7-dibromo-9,9-dialkyl-9H-fluorene (2b) (Scheme S4, Supporting Information).…”

Section: Model Reactionsupporting

confidence: 88%

“…These results are consistent with those of the model reaction (Scheme 1) and the trends observed in the transition‐metal‐catalyzed nonstoichiometric polycondensation and polyaddition. [ 2–9,35 ]…”

Section: Resultsmentioning

confidence: 99%

“…These results are consistent with those of the model reaction (Scheme 1) and the trends observed in the transition-metal-catalyzed nonstoichiometric polycondensation and polyaddition. [2][3][4][5][6][7][8][9]35] Scheme 2. Intramolecular transfer of Pd catalyst on fluorene moiety.…”

Section: Nonstoichiometric Polycondensationmentioning

confidence: 99%

“…[2] Synthesis of high-molecular-weight 𝜋-conjugated polymers has also been demonstrated under nonstoichiometric reaction conditions via the Suzuki-Miyaura or Migita-Kosugi-Stille coupling. [3][4][5][6][7][8][9] Although an excess of dibromoarylene monomer was used in these studies, 𝜋-conjugated polymers with organometallic terminals at both ends were formed. This is attributed to a preference of the intramolecular transfer of the Pd catalyst through dibromoarylene moiety over an intermolecular catalyst transfer, [10,11] which has also been applied to catalyst-transfer condensation polymerization reactions of AB-type monomers.…”

Section: Introductionmentioning

confidence: 99%

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Nonstoichiometric Direct Arylation Polymerization of Octafluorobiphenyl with 2,7‐Diiodofluorene for Regulating CH Terminals of π‐Conjugated Polymer

Takimoto,

Goto,

Chen

et al. 2023

Macromol. Rapid Commun.

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Nonstoichiometric direct arylation polycondensation of 2,2′,3,3′,5,5′,6,6′‐octafluorobiphenyl with excess of 2,7‐diiodo‐9,9‐dioctyl‐9H‐fluorene is demonstrated. Pd/Ag dual‐catalyst system under water/2‐methyltetrahydrofuran biphasic conditions enables direct arylation under mild conditions and promotes the intramolecular transfer of a Pd catalyst walking through the fluorene moiety. The nonstoichiometric direct arylation polycondensation under the optimized reaction conditions produces the corresponding π‐conjugated polymer with a high molecular weight and terminal octafluorobiphenyl units at both ends.

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Section: Model Reactionsupporting

confidence: 88%

Section: Resultsmentioning

confidence: 99%

Section: Nonstoichiometric Polycondensationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Nonstoichiometric Direct Arylation Polymerization of Octafluorobiphenyl with 2,7‐Diiodofluorene for Regulating CH Terminals of π‐Conjugated Polymer

Takimoto,

Goto,

Chen

et al. 2023

Macromol. Rapid Commun.

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“…In the present study, we investigated Suzuki–Miyaura CTCP of a simple acceptor phenylene monomer 2 having two alkoxycarbonyl groups (a terephthalic acid ester derivative) with a t Bu 3 P-ligated Pd initiator 1 , which is often used for Suzuki–Miyaura CTCP . During the course of this work, Higashihara and co-workers reported that the t Bu 3 PPd catalyst undergoes intramolecular catalyst transfer on 2,5-dibromoterephthalic acid ester in Stille coupling reaction with 2-stannylthiophene; however, they have not reported CTCP of an AB-type phenylene monomer with two alkoxycarbonyl groups. We found that the polymerization of pinacol boronate (Bpin) 2a was accompanied by side reactions, whereas the boronic 1,1,2,2-tetraethylethylene glycol ester (B(Epin)) counterpart 2b underwent Suzuki–Miyaura CTCP in the presence of CsF/18-crown-6, which is commonly used as a mild base for Suzuki–Miyaura CTCP of Bpin monomers, affording well-defined n-type polyphenylene.…”

Section: Introductionmentioning

confidence: 99%

Suzuki–Miyaura Catalyst-Transfer Condensation Polymerization for the Synthesis of Polyphenylene with Ester Side Chain by Using Stable, Reactive 1,1,2,2-Tetraethylethylene Glycol Boronate (B(Epin)) Monomer

Nitto,

Ohta,

Yokozawa

2024

Macromolecules

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Suzuki–Miyaura catalyst-transfer condensation polymerization (CTCP) of 4-bromo-2,5-dihexyloxycarbonylphenylboronic acid ester (2) as an acceptor monomer was investigated. The polymerization of the boronic acid pinacol ester (Bpin) monomer (2a) was first conducted in the presence of t Bu3P-ligated tolyl–Pd-Br initiator 1 and CsF/18-crown-6 as a base, affording mainly polymers with H/H ends. We thought that the unsuccessful CTCP of 2a might be due to (1) poor catalyst transfer from the donor initiator unit to the acceptor monomer unit, (2) strong coordination of the Pd catalyst to the alkoxycarbonyl groups on successive repeat units, or (3) nonplanarity of the π-face of the backbone owing to the steric effect of the alkoxycarbonyl groups in the repeat unit. However, model reactions showed that the Pd catalyst successfully underwent intramolecular catalyst transfer, ruling out these possibilities. We then replaced 2a with B(Epin) monomer 2b, which is more stable than 2a. In the polymerization of 2b, the M n value increased in proportion to the monomer conversion and feed ratio of [2b]0/[1]0 and the molecular weight distribution remained narrow. The matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrum showed a series of peaks due to the polymer with Tolyl/H ends. After end-capping of the polymer with 4-methoxyphenylboronic acid, the 1H NMR spectrum exhibited signals of both end groups. These results indicate that the polymerization of 2b proceeded according to the CTCP mechanism.

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High‐Precision Tailored Polymer Molecular Weights for Specific Photovoltaic Applications through Ultrasound‐Induced Simultaneous Physical and Chemical Events

Kim,

Oh,

Park

et al. 2024

Angewandte Chemie

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It is highly challenging to reproducibly prepare semiconducting polymers with targeted molecular weight tailored for next‐generation photovoltaic applications. Once such an easily accessible methodology is established, which can not only contribute to overcome the current limitation of the statistically determined nature of semiconducting polymers, but also facilitate rapid incorporation into the broad synthetic chemists’ toolbox. Here, we describe a simple yet robust ultrasonication‐assisted Stille polymerization for accessing semiconducting polymers with high‐precision tailored molecular weights (from low to ultrahigh molecular weight ranges) while mitigating their interbatch variations. We propose that ultrasound‐induced simultaneous physical and chemical events enable precise control of the semiconducting polymers’ molecular weights with high reproducibility to satisfy all the optical/electrical and morphological demands of diverse types of high‐performance semiconducting polymer‐based devices; as demonstrated in in‐depth experimental screenings in applications of both organic and perovskite photovoltaics. We believe that this methodology provides a fast development of new and existing semiconducting polymers with the highest‐level performances possible on various photovoltaic devices.

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Catalyst-transfer system in stoichiometry-independent AA+BB-type Migita–Kosugi–Stille coupling polycondensation using ester-functionalized dibromo monomer

Cited by 9 publications

References 29 publications

Nonstoichiometric Direct Arylation Polymerization of Octafluorobiphenyl with 2,7‐Diiodofluorene for Regulating CH Terminals of π‐Conjugated Polymer

Nonstoichiometric Direct Arylation Polymerization of Octafluorobiphenyl with 2,7‐Diiodofluorene for Regulating CH Terminals of π‐Conjugated Polymer

Suzuki–Miyaura Catalyst-Transfer Condensation Polymerization for the Synthesis of Polyphenylene with Ester Side Chain by Using Stable, Reactive 1,1,2,2-Tetraethylethylene Glycol Boronate (B(Epin)) Monomer

High‐Precision Tailored Polymer Molecular Weights for Specific Photovoltaic Applications through Ultrasound‐Induced Simultaneous Physical and Chemical Events

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