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Structure and "surfactochromic" properties of conjugated polyelectrolyte (CPE): surfactant complexes between a cationic polythiophene and SDS in water

  • Knaapila, Matti Physics Department, Institute for Energy Technology, Kjeller, Norway
  • Evans, Rachel C. School of Chemistry, Trinity College Dublin, Ireland
  • Garamus, Vasil M. GKSS Research Centre, Geesthacht, Germany
  • Almásy, László Laboratory for Neutron Scattering, PSI, Villigen, Switzerland - Adolphe Merkle Institut, University of Fribourg, Switzerland
  • Székely, Noémi K. Research Institute for Solid State Physics and Optics, Budapest, Hungary
  • Gutacker, Andrea Fachbereich Chemie, Bergische Universitt Wuppertal, Germany
  • Scherf, Ullrich Fachbereich Chemie, Bergische Universitt Wuppertal, Germany
  • Burrows, Hugh D. Departamento de Qumica, Universidade de Coimbra, Portugal
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  • Langmuir. - 2010, vol. 26, no. 19, p. 15634–15643
English We report on the phase transitions, solution structure, and consequent effect on the photophysical properties of poly[3-(6-trimethylammoniumhexyl)thiophene] bromide (P3TMAHT) in aqueous sodium dodecylsulfate (SDS). Polythiophene was mixed with SDS or deuterated SDS to form P3TMAHT(SDS)x complex (x = the molar ratio of surfactant over monomer units) in D₂O and studied by small-angle neutron and X-ray scattering (SANS/SAXS) and optical spectroscopy. At room temperature, P3TMAHT forms charged aggregates with interparticle order. The addition of SDS eliminates the interparticle order and leads to rod-like (x = 1/5) or sheet-like polymer−SDS aggregates (x = 1/2 to 1) containing rod-like (x = 1/5 to 1/2) or sheet-like (x = 1/2 to 1) polymer associations. Partial precipitation occurs at the charge compensation point (x = 1). Ellipsoidal particles without interparticle order, reminiscent of SDS micelles modified by separated polymer chains, occur for x = 2 to 5. Free SDS micelles dominate for x = 20. Structural transitions lead to a concomitant variation in the solution color from red (P3TMAHT) to violet (x = 1/5 to 1) to yellow (x > 2). The photoluminescence fingerprint changes progressively from a broad featureless band (x = 0) through the band narrowing and appearance of vibronic structure (x = 1/5 to 1) to the return to a blue-shifted broad emission band (x = 5). The polymer stiffness reaches a maximum for x = 1, which leads to minimization of the Stokes shift (0.08 eV). This work gives fundamental information upon how surfactant complexation can influence both the solution structure and photophysical properties of a water-soluble polythiophene.
Faculté des sciences et de médecine
Institut Adolphe Merkle
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