Abstract
A water-soluble porphyrin, meso-tetra(4-sulfonatophenyl)porphyrin (TSPP), has been associated with two different polycations, poly(diallyldimethylammonium chloride) (PDDA) and poly(ethyleneimine) (PEI), to investigate the effects of polymer binding upon the TSPP structure and excited-state dynamics both in solution and in ultrathin (∼10−30 A) films deposited on glass slides by electrostatic assembly. Association of the porphyrin with PEI intrinsically quenches the singlet state dynamics of TSPP, both in solution and in films, while quenching is observed upon association with PDDA only for high concentrations of porphyrins or in films where TSPP aggregates are observed. For PDDA:TSPP films without significant aggregate content, the fluorescence decay time (τ1/e ∼ 5−6 ns) approaches that observed for monomeric or polymer-bound porphyrins in dilute solution (τ1/e = 10.2 and 11.3 ns, respectively). However, rapid (<1 ns) deactivation of the singlet states can be observed whenever appreciable aggregates are pr...
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