Influence of Backbone Fluorination in Regioregular Poly(3-alkyl-4-fluoro)thiophenes

Handle URI:
http://hdl.handle.net/10754/598621
Title:
Influence of Backbone Fluorination in Regioregular Poly(3-alkyl-4-fluoro)thiophenes
Authors:
Fei, Zhuping; Boufflet, Pierre; Wood, Sebastian; Wade, Jessica; Moriarty, John; Gann, Eliot; Ratcliff, Erin L.; McNeill, Christopher R.; Sirringhaus, Henning; Kim, Ji-Seon; Heeney, Martin
Abstract:
© 2015 American Chemical Society. We report two strategies toward the synthesis of 3-alkyl-4-fluorothiophenes containing straight (hexyl and octyl) and branched (2-ethylhexyl) alkyl groups. We demonstrate that treatment of the dibrominated monomer with 1 equiv of alkyl Grignard reagent leads to the formation of a single regioisomer as a result of the pronounced directing effect of the fluorine group. Polymerization of the resulting species affords highly regioregular poly(3-alkyl-4-fluoro)thiophenes. Comparison of their properties to those of the analogous non-fluorinated polymers shows that backbone fluorination leads to an increase in the polymer ionization potential without a significant change in optical band gap. Fluorination also results in an enhanced tendency to aggregate in solution, which is ascribed to a more co-planar backbone on the basis of Raman and DFT calculations. Average charge carrier mobilities in field-effect transistors are found to increase by up to a factor of 5 for the fluorinated polymers.
Citation:
Fei Z, Boufflet P, Wood S, Wade J, Moriarty J, et al. (2015) Influence of Backbone Fluorination in Regioregular Poly(3-alkyl-4-fluoro)thiophenes. Journal of the American Chemical Society 137: 6866–6879. Available: http://dx.doi.org/10.1021/jacs.5b02785.
Publisher:
American Chemical Society (ACS)
Journal:
Journal of the American Chemical Society
KAUST Grant Number:
CRG-1-2012-THO-015
Issue Date:
3-Jun-2015
DOI:
10.1021/jacs.5b02785
PubMed ID:
25994804
Type:
Article
ISSN:
0002-7863; 1520-5126
Sponsors:
This work was supported by EPSRC grants EP/G060738/1 and EP/K029843/1, a KAUST Competitive Research grant under agreement no. CRG-1-2012-THO-015, and the Australian Research Council (FT100100275, DP130102616). We thank Dr. Scott E. Watkins (CSIRO Melbourne) for the PESA measurements. Part of this research was undertaken on the SAXS/WAXS beamline at the Australian Synchrotron, Victoria, Australia.
Appears in Collections:
Publications Acknowledging KAUST Support

Full metadata record

DC FieldValue Language
dc.contributor.authorFei, Zhupingen
dc.contributor.authorBoufflet, Pierreen
dc.contributor.authorWood, Sebastianen
dc.contributor.authorWade, Jessicaen
dc.contributor.authorMoriarty, Johnen
dc.contributor.authorGann, Elioten
dc.contributor.authorRatcliff, Erin L.en
dc.contributor.authorMcNeill, Christopher R.en
dc.contributor.authorSirringhaus, Henningen
dc.contributor.authorKim, Ji-Seonen
dc.contributor.authorHeeney, Martinen
dc.date.accessioned2016-02-25T13:33:17Zen
dc.date.available2016-02-25T13:33:17Zen
dc.date.issued2015-06-03en
dc.identifier.citationFei Z, Boufflet P, Wood S, Wade J, Moriarty J, et al. (2015) Influence of Backbone Fluorination in Regioregular Poly(3-alkyl-4-fluoro)thiophenes. Journal of the American Chemical Society 137: 6866–6879. Available: http://dx.doi.org/10.1021/jacs.5b02785.en
dc.identifier.issn0002-7863en
dc.identifier.issn1520-5126en
dc.identifier.pmid25994804en
dc.identifier.doi10.1021/jacs.5b02785en
dc.identifier.urihttp://hdl.handle.net/10754/598621en
dc.description.abstract© 2015 American Chemical Society. We report two strategies toward the synthesis of 3-alkyl-4-fluorothiophenes containing straight (hexyl and octyl) and branched (2-ethylhexyl) alkyl groups. We demonstrate that treatment of the dibrominated monomer with 1 equiv of alkyl Grignard reagent leads to the formation of a single regioisomer as a result of the pronounced directing effect of the fluorine group. Polymerization of the resulting species affords highly regioregular poly(3-alkyl-4-fluoro)thiophenes. Comparison of their properties to those of the analogous non-fluorinated polymers shows that backbone fluorination leads to an increase in the polymer ionization potential without a significant change in optical band gap. Fluorination also results in an enhanced tendency to aggregate in solution, which is ascribed to a more co-planar backbone on the basis of Raman and DFT calculations. Average charge carrier mobilities in field-effect transistors are found to increase by up to a factor of 5 for the fluorinated polymers.en
dc.description.sponsorshipThis work was supported by EPSRC grants EP/G060738/1 and EP/K029843/1, a KAUST Competitive Research grant under agreement no. CRG-1-2012-THO-015, and the Australian Research Council (FT100100275, DP130102616). We thank Dr. Scott E. Watkins (CSIRO Melbourne) for the PESA measurements. Part of this research was undertaken on the SAXS/WAXS beamline at the Australian Synchrotron, Victoria, Australia.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleInfluence of Backbone Fluorination in Regioregular Poly(3-alkyl-4-fluoro)thiophenesen
dc.typeArticleen
dc.identifier.journalJournal of the American Chemical Societyen
dc.contributor.institutionImperial College London, London, United Kingdomen
dc.contributor.institutionUniversity of Cambridge, Cambridge, United Kingdomen
dc.contributor.institutionMonash University, Melbourne, Australiaen
dc.contributor.institutionAustralian Synchrotron, Clayton, Australiaen
dc.contributor.institutionUniversity of Arizona, Tucson, United Statesen
kaust.grant.numberCRG-1-2012-THO-015en

Related articles on PubMed

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