Photophysical Processes in Polymers. VI. Spectroscopic Properties of 1-Vinylpyrene and Poly(1-Vinylpyrene)

Abstract

The absorption spectra, corrected fluorescence spectra, and fluorescence quantum yields of 1‐vinylpyrene and poly(1‐vinylpyrene) are reported. The triplet‐triplet absorptionspectrum of poly(1‐vinylpyrene) is compared to that of pyrene, and the excimer fluorescence of the polymer is studied as a function of temperature. Based upon the temperature dependence of the excimer emission, it is concluded that efficient formation and inefficient emission of nonequilibrium‐geometry pyrene excimers takes place in poly(1‐vinylpyrene). Radiative and radiationless transition mechanisms are discussed. Values reported for poly(1‐vinylpyrene) in fluid solution at room temperature are q FM ≅ 0, q FD = 0.44, q PM ≅ 0, φ T = 0.005, k FD = 0.83 × 10 7 sec −1 , k GD = 1.0 × 10 7 sec −1 , k DM >∼ 1 × 10 7 sec −1 , and k TM <∼ 5 × 10 5 sec −1 .