Observation of super-Nernstian proton-coupled electron transfer and elucidation of nature of charge carriers in a multiredox conjugated polymer

Tran, Duyen K.; West, Sarah M.; Speck, Elizabeth M. K.; Jenekhe, Samson A.

doi:10.1039/d4sc00785a

Cited by 2 publications

(2 citation statements)

References 71 publications

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“…In the polymer, protonated bis-perimidine segments are present due to hydrogen bonding interactions with the C=O group. These interactions can manifest in different forms, including the possibility of proton transfer to generate an hydroxy group, as demonstrated in this study 36 .…”

Section: Mechanism Of Electrochemical Reactionsmentioning

confidence: 75%

Investigating Perimidine Precursors for the Synthesis of New Multiredox Polymers

Janasik,

Chulkin,

Czichy

et al. 2024

Preprint

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We present a new simple approach for electrochemical synthesis of semi-condensed ambipolar perinone polymers with phthaloperine (p1) or phenanthroline (p2) skeleton from available and cheap perimidine precursors. Polymerization of perimidine derivatives varies in efficiency depending on the monomer, but overall is highly efficient, especially when electropolymerization is used. Electrooxidation is well controllable and provides a certain characteristic share of new bonds in the structure of perimidine polymers: semi-ladder bis-perimidine unit, ladder bis-perimidine unit, and protonated bis-perimidine unit. Polymer p2 obtained with higher efficiency was put through broader analysis (UV-Vis, IR, ESR and quantum-chemical calculations). As indicated, donor-acceptor structure and specific intermolecular interactions of p2 assure its electrical conductivity and complex redox activity. Although protonated bonds break π-conjugation in the structure of the macromolecule, there is also a diradical state that favors intermolecular interactions and intermolecular π-conjugation channels within bis-perimidine segments. It has been proven that there is a diradical state which appears as an intermediate state between the oxidized and reduced states of the protonated polymer unit. This work positions perimidine polymers as a versatile ambipolar multiredox p- and n-type conductor, indicating a potential for expanding perinone-based perylene-diperimidine polymers for innovative electronics and (bio)sensors.

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Section: Mechanism Of Electrochemical Reactionsmentioning

confidence: 75%

Investigating Perimidine Precursors for the Synthesis of New Multiredox Polymers

Janasik,

Chulkin,

Czichy

et al. 2024

Preprint

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“…85 An n-type derivative of BBL that features a phenazine moiety, BBL-P, has recently shown novel features, including "super-Nernstian" protoncoupled electron transfer reactions. 86,87 There are clearly many advantages of ladder polymers such as LTBT, which include facile, scalable synthesis and processability into high-quality thin films for device applications. In particular, we believe that the narrow bandgap and strong donor−acceptor character of LTBT makes it an attractive p-type semiconducting polymer for solar cell applications.…”

Section: Synthesis and Characterization Of Ltbt And Tbbtmentioning

confidence: 99%

Conjugated Ladder Poly(thienobenzothiazine): Synthesis, Electronic Structure, Optical Properties, and Electrical Conductivity of a Narrow Bandgap p-Type Semiconducting Polymer

West,

Tran,

Kaminsky

et al. 2024

Macromolecules

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We report herein the synthesis, electronic structure, experimental and density functional theory (DFT) calculated optical properties, and electrical conductivity of a new π-conjugated ladder polymer, ladder poly(thienobenzothiazine) (LTBT), and its model compound, thienobis(benzothiazine) (TBBT). The synthesis of LTBT in a mixed polyphosphoric acid/sulfolane solvent system gave an intrinsic viscosity of 2.0 dL/g at 30 °C in methanesulfonic acid, and the polymer could form large-area freestanding films. Single-crystal X-ray structure of TBBT showed that it crystallizes in an orthorhombic structure with a coplanar thienobenzothiazine ladder backbone, which is in agreement with the DFT calculated structure. The electrochemically derived HOMO and LUMO energy levels of −5.17 eV and −3.75 eV of LTBT thin films revealed the p-type semiconducting nature of the conjugated ladder polymer. We thus p-doped LTBT thin films with FeCl3, leading to an average electrical conductivity of 0.3 S/cm. These results demonstrate the potential of the new ladder polymer LTBT in organic electronics while providing valuable insights into the structure–property relationships of semiconducting ladder polymers.

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Observation of super-Nernstian proton-coupled electron transfer and elucidation of nature of charge carriers in a multiredox conjugated polymer

Abstract: Nernstian proton-coupled electron transfer (PCET) is a fundamental process central to many physical and biological systems, such as electrocatalysis, enzyme operation, DNA biosynthesis, pH-/bio-sensors, and electrochemical energy storage devices. We...

Cited by 2 publications

References 71 publications

Investigating Perimidine Precursors for the Synthesis of New Multiredox Polymers

Investigating Perimidine Precursors for the Synthesis of New Multiredox Polymers

Conjugated Ladder Poly(thienobenzothiazine): Synthesis, Electronic Structure, Optical Properties, and Electrical Conductivity of a Narrow Bandgap p-Type Semiconducting Polymer

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