KINETICS OF EXCIMER FORMATION IN POLY(1-NAPHTHYL METHACRYLATE)

In poly (1-naphthyl methacrylate) the excimer to monomer ratio, Ie/Im, is greatest in a poor (chain contracting) solvent and at high molecular weight. However, in poly(l-naphthyl acrylate), this ratio is virtually independent of solvent. This effect is discussed in terms of the increased chain flexibility and the existence of nearest neighbor interactions in the acrylate polymer. Binding energies of the PNMA excimer were estimated from steady-state measurements and range from 3 to 5 kcal/mol in various solvents. Transient measurements by single photon time correlation spectroscopy show that the rate of excimer formation, KDM, follows an Arrhenius rate law, with an activation energy of about 3 kcal/mol. Evidence is presented suggesting a correlation between fcDM and the rate of rotational relaxation of several polymers. © 1979, American Chemical Society. All rights reserved.