Poly(4,4'-p-phenylenebis[2,6-diphenyl]pyridinium-alt-bisparaphenylene ditetrafluoroborate) and a model compound exhibit fluorescence emission from dilute solutions in dimethylformamide and vitrified samples dispersed in glassy poly(methyl methacrylate). The excitation and emission spectra, excitation polarization spectra and quantum yields for fluorescence were characterized in the dilute solution limit in dimethylformamide. Strong depolarization of the fluorescence was observed in dilute solution. The time-dependent decays of the intensity of the fluorescence were analysed to determine the lifetimes of the singlet excitation. In order to assist in the interpretation of the experiments, the conformations and molecular dynamics were investigated for an isolated dimer in the electronic ground state. The minimum energy conformations were found to be similar to those populated by other ortho-phenyl substituted para-phenylene structures in the solid state. The molecule experiences frequent transitions between rotational isomers that involve changes in dihedral angles in the main chain and between the main chain and pendant phenyl groups. The trajectory shows that there are correlations in these conformational transitions. The depolarization is attributed to an intramolecular non-radiative energy transfer mechanism coupled with frequent conformational changes in the main chain and pendant group torsional angles during the lifetime of the singlet excited state.
Посилання на статтю:
Characterization of rigid rod poly(pyridinium salt)s by conformational analysis, molecular dynamics, and steady-state and time resolved fluorescence / Michael P. Makowski* and Wayne L. Mattice // Polymer. – 1993. – Vol 34. – P. 1606-1612.