TY - JOUR
T1 - Mapping and Tuning the Fluorescence of Perfluorinated Polyanilines Synthesized through Liquid–Liquid Interfaces
AU - Dallas, Panagiotis
AU - Rasovic, Ilija
AU - Porfyrakis, Kyriakos
PY - 2016/3/10
Y1 - 2016/3/10
N2 - A series of light-emitting perfluorinated polyanilines were synthesized by the oxidative polymerization of 3-perfluorooctyl aniline through a variety of aqueous/organic interfaces. According to the interfacial tension between the two solvents (the organic being chloroform, dichloromethane, perfluorinated ether, toluene, or o-dichlorobenzene), we obtain distinctive classes of materials based on the crystal packing, protonation, and oxidation state of the polymeric chains. We distinguish between soluble fractions with a distinctive, strong, and red-shifted photoluminescence pattern and an insoluble precipitate which can be subsequently solubilized in a mixture of acetone and toluene. The emission maximum for the insoluble fraction is located in the ultraviolet or blue region with a small Stokes shift; maxima for the soluble counterparts are in the green to yellow region. The soluble derivatives demonstrate a significantly smaller band gap compared to the monomer and large Stokes shifts up to 163 nm; the emission maximum for the most red-shifted emission was located at λem = 548 nm. Their redox activity toward silver nanoparticles, their sensor reactivity with organic acid and bases, and the subsequent changes in the optical properties were demonstrated and the structure of the materials was evaluated with NMR, X-ray diffraction, and FTIR/Raman spectroscopy.
AB - A series of light-emitting perfluorinated polyanilines were synthesized by the oxidative polymerization of 3-perfluorooctyl aniline through a variety of aqueous/organic interfaces. According to the interfacial tension between the two solvents (the organic being chloroform, dichloromethane, perfluorinated ether, toluene, or o-dichlorobenzene), we obtain distinctive classes of materials based on the crystal packing, protonation, and oxidation state of the polymeric chains. We distinguish between soluble fractions with a distinctive, strong, and red-shifted photoluminescence pattern and an insoluble precipitate which can be subsequently solubilized in a mixture of acetone and toluene. The emission maximum for the insoluble fraction is located in the ultraviolet or blue region with a small Stokes shift; maxima for the soluble counterparts are in the green to yellow region. The soluble derivatives demonstrate a significantly smaller band gap compared to the monomer and large Stokes shifts up to 163 nm; the emission maximum for the most red-shifted emission was located at λem = 548 nm. Their redox activity toward silver nanoparticles, their sensor reactivity with organic acid and bases, and the subsequent changes in the optical properties were demonstrated and the structure of the materials was evaluated with NMR, X-ray diffraction, and FTIR/Raman spectroscopy.
U2 - 10.1021/acs.jpcb.6b00739
DO - 10.1021/acs.jpcb.6b00739
M3 - Article
SN - 1089-5647
VL - 120
SP - 3441
EP - 3454
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 13
ER -