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Cationic ionene as n-dopant agent of poly(3,4-ethylenedioxythiophene)


We report the reduction of poly(3,4-ethylenedioxythiophene) (PEDOT) films with a cationic 1,4-diazabicyclo[2.2.2]octane-based ionene bearing N,N’-(meta-phenylene)dibenzamide linkages (mPI). Our main goal is to obtain n-doped PEDOT using a polymeric dopant agent rather than small conventional tetramethylammonium (TMA), as is usual. This has been achieved using a three-step process, which has been individually optimized: (1) preparation of p-doped (oxidized) PEDOT at a constant potential of +1.40 V in acetonitrile with LiClO4 as electrolyte; (2) dedoping of oxidized PEDOT using a fixed potential of –1.30 V in water; and (3) redoping of dedoped PEDOT applying a reduction potential of –1.10 V in water with mPI. The resulting films display the globular appearance typically observed for PEDOT, mPI being structured in separated phases forming nanospheres or ultrathin sheets. This organization, which has been supported by atomistic Molecular Dynamics simulations, resembles the nanosegregated phase distribution observed for PEDOT p-doped with poly(styrenesulfonate). Furthermore, the doping level achieved using mPI as doping agent is comparable to that reached with TMA, even though the ionene provides distinctive properties to the conducting polymer. For example, films redoped with mPI exhibit much more hydrophilicity than the oxidized ones, whereas films redoped with TMA are hydrophobic. Similarly, films redoped mPI exhibit the highest thermal stability, while those redoped with TMA show a thermal stability that is intermediate between the latter and dedoped PEDOT. Overall, the incorporation of mPI polycation as n-dopant into PEDOT has important advantages for modulating the properties of this emblematic conducting polymer.

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Publication details

The article was received on 22 Nov 2017, accepted on 12 Mar 2018 and first published on 12 Mar 2018

Article type: Paper
DOI: 10.1039/C7CP07878A
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
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    Cationic ionene as n-dopant agent of poly(3,4-ethylenedioxythiophene)

    M. C. G. Saborio, O. Bertran, S. Lanzalaco, M. Haering, D. Díaz Díaz, F. Estrany and C. Aleman, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C7CP07878A

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