Intramolecular energy transfer by singlet and triplet excitons in macromolecules

Absorption, luminescence and photo-oxidation of polyvinylcarbazole (PVCa) and polyvinylbenzocarbazole (PVBCa) in weak solutions have been studied. It is found that fluorescence and phosphorescence spectra, observed at 293, 77 and 4.2 K, depend on the molecular mass M of the polymer and on the experimental conditions. Due to efficient intramolecular energy transfer the fluorescence spectrum includes the emission of excimers, emission of end groups and that of internal structural defects of a macrochain. The relative role of each emission markedly depends on M. Phosphorescence is largely determined by the annihilation effects between triplet excitations, these effects being pronounced in long macrochains. The data show the excitonic nature of the singlet and triplet excitation energy transfer in the polymers studied. The migration of one-dimensional singlet and triplet excitons strongly influences the luminescent properties of PVCa and PVBCa macromolecules, as well as their photochemical reactions. The range of singlet excitons in PVCa and PVBCa macromolecules is determined both at room temperature and at low temperatures.