Heavy atom substitution — A strategy for improving conductivity in conjugated polymers

Panchuk, Jenny R.; Laramée, Arnaud W.; Manion, Joseph G.; Ye, Shuyang; Seferos, Dwight S.

doi:10.1016/j.synthmet.2019.04.023

Cited by 15 publications

(28 citation statements)

References 19 publications

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“…45,46 Polychalcogenophene oxidation, or oxidative doping, results in cations delocalized along the polymer backbone, which improves their chargetransport properties in functional materials. 42,47 Importantly, p-conjugated polymer oxidative doping also induces aggregation and precipitation from solution, 48,49 a feature which we realized could be exploited to promote self-assembly.…”

Section: Introductionmentioning

confidence: 82%

“…41 In addition, PTes have an oxidation potential $0.2 eV higher than PThs, allowing the polymer to be oxidized more readily than other polychalcogenophenes. 42 Polychalcogenophenes possess other attractive features; regioregular polychalcogenophenes will crystallize, 43,44 which narrows their electronic band gap and increases their oxidation potential. 45,46 Polychalcogenophene oxidation, or oxidative doping, results in cations delocalized along the polymer backbone, which improves their chargetransport properties in functional materials.…”

Section: Introductionmentioning

confidence: 99%

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Oxidation promoted self-assembly of π-conjugated polymers

et al. 2020

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Section: Introductionmentioning

confidence: 82%

Section: Introductionmentioning

confidence: 99%

Oxidation promoted self-assembly of π-conjugated polymers

et al. 2020

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“…[33] Experimentally, doped chalcogens can attain similar levels of conductivity to one another; however, heavier heteroatoms require less dopant. [34] The cationic HOMO and LUMO diagrams (inset in Figure 5) reveal an identical distribution of electron density relative to the neutral HOMO and LUMO diagrams. HOMO electron density is concentrated on bonds 1 and 3, whereas LUMO electron density is concentrated on bonds 2 and 4.…”

Section: Radical Cationsmentioning

confidence: 90%

“…These trends line up well with experimental work, specifically doping studies on polychalcogenophenes, where the identity of the heteroatom influences the oxidation potential but not necessarily the overall conductivity of the charged species. [19,[33][34] There is clear merit for further theoretical and experimental studies on heteroatom substitution, particularly involving the heavier atoms. A thorough understanding of how heteroatoms influence the properties of conjugated polymers will enable the future design of electronic materials tailored to their specific application.…”

Section: Discussionmentioning

confidence: 99%

Trends in Conjugated Chalcogenophenes: A Theoretical Study

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Cheng

et al. 2021

Chemistry A European J

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Heavy atom substitution in chalcogenophenes is a versatile strategy for tailoring and ultimately improving conjugated polymer properties. While thiophene monomers are commonly implemented in polymer designs, relatively little is known regarding the molecular properties of the heavier chalcogenophenes. Herein, we use density functional theory (DFT) calculations to examine how group 16 heteroatoms, including the radioactive polonium, affect polychalcogenophene properties including bond length, chain twisting, aromaticity, and optical properties. Heavier chalcogenophenes are more quinoidal in character and consequently have reduced band gaps and larger degrees of planarity. We consider both the neutral and radical cationic species. Upon p-type doping, bond length rearrangement is indicative of a more delocalized electronic structure, which combined with optical calculations is consistent with the polaron-model of charge storage on conjugated polymer chains. A better understanding of the properties of these materials at their molecular levels will inevitably be useful in material design as the polymer community continues to explore more main group containing polymers to tackle issues in electronic devices.

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“…When doped with F4TCNQ via SqP, charge carrier concentration only increases a small amount across the series whereas conductivity increases dramatically with increasing selenophene content. Using Hall Effect measurements, they found that the conductivity increase arises from increased Hall mobility due to increased crystallinity.Gregory et al and Panchuk et al took a different approach by synthesising a series of poly(3-alkylchalcogenophenes) with sulphur, selenium and tellurium and 3,7-dimethyloctyl as the side chain (Gregory et al, 2018;Panchuk et al, 2019). Dip-doping in low concentrations of FeCl3 and Fe(Tos)3 revealed moderate doping efficiencies and electrical conductivities when moving down group 16, showing that using the heavier chalcogens is a promising strategy to increase electrical conductivity.…”

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confidence: 99%