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3,4-Phenylenedioxythiophenes (PheDOTs) functionalized with electron-withdrawing groups and their analogs for organic electronics. Remarkably efficient tuning the energy levels in flat conjugated polymers

Abstract

A novel, facile and efficient one-pot microwave-assisted method of synthesis allowing an access to a new series of 3,4-phenylenedioxy-thiophene derivatives with electron-withdrawing groups at the benzene ring (EWG-PheDOT) and their analogs (with expanded side π-system or with heteroaromatic rings, ArDOT) by reaction of 2,5-dialkoxycarbonyl-3,4-dihydroxythiophenes with electrophilic aromatic/heteroaromatic compounds in dipolar aprotic solvents has been described. Its applicability to a wide range of novel functionalized ArDOTs as promising building blocks for organic electronic materials have been demonstrated. The structures of selected ArDOTs have been determined by a single crystal X-ray diffraction. The electronic structure of conjugated polymers p[ArDOTs] based on synthesized novel thiophene monomers has been studied theoretically by DFT PBC/B3LYP/6-31G(d) method. The performed calculations reveal that while the side functional groups are formally not in conjugation with the polymer main chain, they have an unprecedentedly strong effect on the HOMO/LUMO energy levels of conjugated polymers, allowing their efficient tuning by over 1.6 eV range. In contrast to that, the energy gaps of the polymers are almost unaffected by such functionalizations and vary within a range of only ≤ 0.05 eV. Computational predictions have been successfully confirmed in experiments: cyclic voltammetry shows a strong anodic shift of p-doping for the electron-withdrawing CF3 group functionalized polymer p[4CF3-PheDOT] relative to the unsubstituted p[PheDOT] polymer (by 0.55 V; DFT predicted decrease of HOMO by 0.58 eV), while very similar Vis-NIR absorption spectra for both polymers in the undoped state indicate that their optical energy gaps near coincide (ΔEg <0.04 eV).

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Publication details

The article was received on 16 Nov 2017, accepted on 02 Jan 2018 and first published on 03 Jan 2018


Article type: Paper
DOI: 10.1039/C7TC05227H
Citation: J. Mater. Chem. C, 2018, Accepted Manuscript
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    3,4-Phenylenedioxythiophenes (PheDOTs) functionalized with electron-withdrawing groups and their analogs for organic electronics. Remarkably efficient tuning the energy levels in flat conjugated polymers

    M. Krompiec, S. N. Baxter, E. L. Klimareva, D. S. Yufit, D. G. Congrave, T. K. Britten and I. F. Perepichka, J. Mater. Chem. C, 2018, Accepted Manuscript , DOI: 10.1039/C7TC05227H

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