Excited-State Dynamics in Rigid Media: Evidence for Long-Range Energy Transfer

In semirigid PEG-DMA550 films with the added anthracene derivatives PEG-An and Acr-An, energy transfer quenching of the metal-to-ligand charge transfer excited state Ru(bpy)(3)(2+)* to give -(3)An occurs by both rapid, static, and slow, diffusional quenching processes. The appearance of -(3)An was verified by transient absorption measurements. The kinetics of the two quenching processes have been analyzed by a Stern-Volmer kinetic analysis. The data for static quenching are consistent with energy transfer quenching with a distance dependence consistent with Dexter (exchange) energy transfer. On the basis of this analysis Bohr radii were found to be 26 and 11 angstrom for PEG-An and Acr-An, respectively. Evidence for triplet-triplet annihilation between triplet anthracene excited states in the films was obtained from the concentration dependences of excited-state decay. These results provide evidence for long-range energy migration between derivatized anthracenes in rigid, cross-linked PEG-DMASSO films.