Mixed Chromophore Perfluorocyclobutyl (PFCB) Copolymers for Tailored Light Emission

Versatile intermediates 4-bromo(trifluorovinyloxy)benzene or 4-trifluorovinyloxyphenylboronic acid pinacol ester undergo a one step Suzuki coupling reaction with commercial aryl diboronic acids or aryl dibromides and afforded three new aryltrifluorovinylether chromophore monomers. The structures of these monomers were confirmed by 1H, 19F, and 13C NMR spectroscopy and elemental (C, H, and N) combustion analysis. The monomers were readily polymerized via thermal [2 + 2] cyclopolymerization to form chromophore containing PFCB polymers with high molecular weights (Mn = 16 700−22 000), superb thermal stability T d > 450 °C, and excellent processability. Photoluminescence studies reveal that the fluorinated ether linkage has no effect on lumiphore emission wavelength or solution quantum yields. Copolymerization affords a facile route to tailored emission from a linear polymeric system that includes a broad range of the visible spectrum. The properties of these polymers were analyzed by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), gel permeation chromatography (GPC), and absorbance and photoluminescence spectroscopy.