STUDIES OF THE ANTENNA EFFECT IN POLYMER-MOLECULES .17. SYNTHESIS AND PHOTOCATALYTIC ACTIVITY OF POLY(SODIUM STYRENE-SULFONATE-CO-N-VINYLCARBAZOLE) AND POLY[SODIUM STYRENE-SULFONATE-CO-N-(ACRYLOYLOXYHEXYL)CARBAZOLE]

Two new antenna polyelectrolytes, poly(sodium styrenesulfonate-co-N-vinylcarbazole) (PSSS-VCz) and poly[sodium styrenesulfonate-co-N-(acryloyloxyhexyl)carbazole] (PSSS-AHCz) have been synthesized. Both polymers were found to solubilize large hydrophobic compounds such as perylene in aqueous solution, but PSSS-AHCz was much more efficient than PSSS-VCz. The distribution coefficients of perylene between the polymer pseudophase and water was determined to be (2.9 +/- 0.1) X 10(6) and (4.0 +/- 0.2) X 10(4) in PSSS-AHCz and PSSS-VCz, respectively. The greater solubilizing ability of PSSS-AHCz is attributed to the higher content of hydrophobic monomer units in the polymer. Both copolymers displayed photocatalytic activity, absorbing light in the UV-visible spectral region. Energy can then be transferred to a solubilized molecule or dissolved oxygen and induce photochemical reactions. The model reaction used in this study was the photosensitized oxidation of perylene solubilized in aqueous polymer solutions. PSSS-AHCz was found to be a much more efficient photocatalyst than PSSS-VCz. The enhanced photocatalytic activity of PSSS-AHCz is attributed to the greater concentration of carbazole chromophores, the higher local concentration of probe in the polymeric pseudophase and possibly to the elimination of the low-energy excimer.