Raman Spectroscopic Studies of Polyfluorenes

Polyfluorenes reveal a complex interplay between emissive properties and intraand intermolecular structure. Vibrational frequencies and intensities determined by Raman spectroscopy are strongly influenced by variations in the backbone as well as side chain conformations. Changes in the structural and electronic properties of two side group substituted polyfluorenes (PF): ethyl-hexyl substituted PF (PF2/6) and dioctyl substituted PF (PF8) as a function of solvent, thermal cycling, and hydrostatic pressure via Raman scattering are presented. The vibrational frequencies and intensities of fluorene oligomers with various alkyl side chain conformations are calculated using hybrid density-functional theory. A comparison of the computed vibrational spectra of single chain fluorene oligomers with our experimental data shows that the conformational isomers in PF8 are a direct consequence of the side chain conformation.