Synthesis of soluble, air-stable fully conjugated ladder polymers

Hirano, Tetsufumi; Hanamura, Hitoshi; Inoue, Munenori; Ueda, Saori; Watanabe, Minoru; Tanabiki, Masao; Mikami, K.

doi:10.1016/j.polymer.2019.06.014

Cited by 8 publications

(3 citation statements)

References 17 publications

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“…The insolubility and poor film-forming properties severely limit their use in thin film polymer electronic applications. Moreover, electronic properties of conjugated polymers are highly dependent on their molecular weight and often a high-molecular weight is deemed beneficial for not only charge transport but also mechanical properties of their thin films or fibers. − Synthetic chemists have found ways to go around these issues by incorporating long solubilizing and/or bulky groups to make these polymers solution processable. ,,− This strategy is often a multistep reaction scheme that relies on the synthesis of the prepolymer, followed by intramolecular ring-closure reactions. More often than not, this strategy has to deal with other various synthetic challenges that render it not any less complex than those without the solubilizing groups. , …”

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confidence: 99%

Facile Synthesis of Solubilizing a Group-Free, Solution-Processable p-Type Ladder Conjugated Polymer and Its Thermoelectric Properties

et al. 2021

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Here we report the synthesis of a new solubilizing group-free, solution-processable p-type ladder conjugated polymer, 6H-pyrrolo[3,2-b:4,5-b′]bis [1,4]benzothiazine ladder (PBBTL) polymer by using a polyphosphoric acid (PPA) and phenylphosphonic acid (PhPO 3 H 2 ) 1:1 binary acid solvent system together with careful control of reaction kinetics. With a good intrinsic viscosity of 3.69 dL/g in methanesulfonic acid (MSA), good quality PBBTL films can be obtained via spin-coating. Intrinsic thin film properties and thermoelectric performance of PBBTL were evaluated, making it the second solubilizing group-free, solution-processable ladder-type conjugated polymer after BBL to be used for thin-film polymer electronics. While our preliminary thermoelectric performance of the FeCl 3 -doped PBBTL films is modest, we believe that many opportunities lie ahead for PBBTL and hope that its successful synthesis using the new PPA:PhPO 3 H 2 binary acid solvent system will inspire synthetic organic chemists to relook into solubilizing group-free, solution-processable ladder-type conjugated polymer systems.

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confidence: 99%

Facile Synthesis of Solubilizing a Group-Free, Solution-Processable p-Type Ladder Conjugated Polymer and Its Thermoelectric Properties

et al. 2021

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“…Recently, Mikami and coworkers successfully incorporated benzothieno[3,2,– b ]benzothiophene (BTBT) repeat unit, one of the promising small molecules in organic electronics, into cLP backbone via the Scholl oxidation [31] . In addition, Takagi and coworker prepared anthracene‐fluorene‐based cLP via the Gilch polymerization of bis(halomethyl)benzene in the presence of an excess base, followed by stepwise Scholl oxidation [32] …”

Section: Review/discussionmentioning

confidence: 99%

Recent Progress in Synthesis of Conjugated Ladder Polymers

Lee

2023

Asian J Org Chem

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Conjugated ladder polymers (cLPs) are macromolecules consisting of fully fused aromatic backbones, which have emerged as an intriguing research area due to their unique electronic and optoelectronic properties. They possess a highly ordered, ladder‐like structure, which leads to improved charge transport properties and enhanced stability compared to conventional conjugated polymers. The synthesis of cLPs involves two main strategies: single‐step ladderization and stepwise ladderization. However, due to the extremely low solubility of the desired cLPs and the limited synthetic methods for preparing defect‐free cLPs, the field of solution‐based synthesis and processing of cLPs encountered synthetic and processing challenges. This review provides an overview of recent achievements in the synthesis of conjugated ladder polymers, emphasizing the challenges and potential in this fascinating field of research.

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“…These advantageous features render conjugated ladder polymers great potential in organic electronic devices including organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), , organic electrochemical transistors (OECTs), , organic thermoelectrics (OTEs), − lithium-ion batteries (LIBs), − photocatalysts, , graphene nanoribbons, , and solar cells. , However, the efficient synthesis and structural characterization of these materials are challenging for further application and development due to their extremely poor solubility in conventional solvents, including tetrahydrofuran (THF), chloroform, chlorobenzene, dimethylformamide (DMF), and N -methylpyrrolidone (NMP). The classical strategy is to introduce solubilizing groups to the backbone for improving solubility and processability. − However, this strategy usually needs to go through multiple-step synthesis via a prepolymer intermediate and further ring closure to form final ladder polymers. Even using such strategy does not necessary guarantee full solubility of the resulting ladder polymers as cross-linking may occur during the ring closure step …”

Section: Introductionmentioning

confidence: 99%

Thermoelectric Performance Enhancement of p-Type Pyrrolo[3,2-b:4,5-b′]bis[1,4]benzothiazine Conjugated Ladder Polymer by Pendant Group Engineering

He,

Wang,

Dexter Tam

et al. 2023

ACS Materials Lett.

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Organic thermoelectrics have attracted widespread attention due to the possibility of harnessing ambient thermal energy to power Internet-of-things and wearables due to their flexibility, low cost, and large-scale production, but research progress still lags behind that of inorganic materials. Rigid ladder-type conjugated polymers consisting of doublestranded fused-ring structure exhibit excellent thermal and electrochemical stabilities and thus are promising materials for organic thermoelectrics. However, effective synthesis, characterization, and solution processing are challenging and thus limit its application in thin-film devices. Here, two p-type pyrrolo[3,2b:4,5-b′]bis [1,4]benzothiazine ladder-type conjugated polymers with different pendant groups (methyl: PBBTL-CH 3 and phenyl: PBBTL-Ph) were synthesized, and both can be solution-processed for thin-film thermoelectric applications. PBBTL-CH 3 achieved electrical conductivities as high as 36.29 ± 0.58 S cm −1 and power factors up to 22.7 ± 2.1 μW m −1 K −2 when doped with FeCl 3 , which are significantly higher than of PBBTL-Ph with a conductivity of 1.40 ± 0.16 S cm −1 and a power factor of 1.7 ± 0.2 μW m −1 K −2 . Grazing-incident wide-angle X-ray scattering of the polymers showed PBBTL-CH 3 exhibited exclusive edge-on orientation, while PBBTL-Ph exhibited mixed edge-on and face-on orientation. The present study indicates that pendant groups have important influence on the electrical conductivity and thermoelectric performance for the PBBTL series through alteration of HOMO energy levels, polymer packing, and ease of dopant infiltration.

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Synthesis of soluble, air-stable fully conjugated ladder polymers

Cited by 8 publications

References 17 publications

Facile Synthesis of Solubilizing a Group-Free, Solution-Processable p-Type Ladder Conjugated Polymer and Its Thermoelectric Properties

Facile Synthesis of Solubilizing a Group-Free, Solution-Processable p-Type Ladder Conjugated Polymer and Its Thermoelectric Properties

Recent Progress in Synthesis of Conjugated Ladder Polymers

Thermoelectric Performance Enhancement of p-Type Pyrrolo[3,2-b:4,5-b′]bis[1,4]benzothiazine Conjugated Ladder Polymer by Pendant Group Engineering

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