Variable-temperature time-resolved emission spectra studies of random pyrene urethane methacrylate copolymers with high pyrene incorporation.

A series of random co-polyurethane methacrylate comb polymers with pyrene (Py) and 3-pentadecylphenol (PDP) as pendant units were prepared by free radical polymerization. The pyrene labeling was varied from 1 to 100 mol %. The excimer emission of these copolymers were studied as a function of both time and temperature using time-resolved emission spectra (TRES) experiments and variable-temperature steady-state fluorescence measurements. Variable-temperature steady-state as well as decay experiments showed that the contribution from excimers via diffusional encounters increased at the cost of pyrene monomer as the temperature increased until ∼50 °C; beyond which nonradiative losses predominated. TRES collected at 25 and 70 °C were compared to study the nature and origin of emitting species as a function of pyrene loading. TRES at 25 °C clearly indicated the presence of ground-state pyrene dimers with emission centered at ∼435 nm which soon gave way to emission centered around 465 and 485 nm in the time-gated spectra collected at higher time intervals. In TRES collected at 70 °C, excimer emission centered at 465 and 485 nm was very high even at short time scales. The lowest pyrene loaded polymer PIHPDP-1Py did not exhibit excimer emission in the TRES collected at 25 °C as well as 70 °C.