Please use this identifier to cite or link to this item: http://hdl.handle.net/10995/102013
Title: 3,4-Phenylenedioxythiophenes (PheDOTs) functionalized with electron-withdrawing groups and their analogs for organic electronics
Authors: Krompiec, M. P.
Baxter, S. N.
Klimareva, E. L.
Yufit, D. S.
Congrave, D. G.
Britten, T. K.
Perepichka, I. F.
Issue Date: 2018
Publisher: Royal Society of Chemistry
Citation: 3,4-Phenylenedioxythiophenes (PheDOTs) functionalized with electron-withdrawing groups and their analogs for organic electronics / M. P. Krompiec, S. N. Baxter, E. L. Klimareva, et al. — DOI 10.1039/c7tc05227h // Journal of Materials Chemistry C. — 2018. — Vol. 6. — Iss. 14. — P. 3743-3756.
Abstract: A novel, facile and efficient one-pot, microwave-assisted method of synthesis allowing an access to a new series of 3,4-phenylenedioxythiophene derivatives with electron-withdrawing groups at the benzene ring (EWG-PheDOT) and their analogs (with an expanded side π-system or with heteroaromatic rings, ArDOT) by the reaction of 2,5-dialkoxycarbonyl-3,4-dihydroxythiophenes with electrophilic aromatic/heteroaromatic compounds in dipolar aprotic solvents has been described. Its applicability over a wide range of novel functionalized ArDOTs as promising building blocks for organic electronic materials has been demonstrated. The structures of selected ArDOTs have been determined by single-crystal X-ray diffraction. The electronic structure of conjugated polymers p[ArDOTs] based on synthesized novel thiophene monomers has been studied theoretically by the 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 the range of 1.6 eV. 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 the decrease of the 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 nearly coincide (ΔEg < 0.04 eV). © 2018 The Royal Society of Chemistry.
Keywords: CYCLIC VOLTAMMETRY
ELECTRONIC STRUCTURE
ENERGY GAP
SINGLE CRYSTALS
X RAY DIFFRACTION
COMPUTATIONAL PREDICTIONS
DIPOLAR APROTIC SOLVENT
ELECTRON WITHDRAWING GROUP
ELECTRONWITHDRAWING
FUNCTIONALIZED POLYMERS
MICROWAVE-ASSISTED METHODS
ORGANIC ELECTRONIC MATERIALS
SINGLE CRYSTAL X-RAY DIFFRACTION
CONJUGATED POLYMERS
URI: http://hdl.handle.net/10995/102013
Access: info:eu-repo/semantics/openAccess
SCOPUS ID: 85045076466
PURE ID: 7028069
ea064a6b-a188-421a-a510-7f1c788409c4
ISSN: 20507534
DOI: 10.1039/c7tc05227h
Appears in Collections:Научные публикации, проиндексированные в SCOPUS и WoS CC

Files in This Item:
File Description SizeFormat 
2-s2.0-85045076466.pdf15,79 MBAdobe PDFView/Open


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.