Magnetic field effects on triplet exciton fission and fusion in a polydiacetylene

We have studied the origin and decay dynamics of triplet excitons in the conjugated polymer poly(4BCMU) in its sol(yellow) and gel(red) phases. Wavelength and intensity dependencies of the triplet yield show that the triplet exciton cannot be produced by excitation into the singlet exciton edge but only from higher lying states. The observed lifetime of the triplet state, coupled with the magnetic field dependence of the triplet state production and decay, indicate that the triplet state is created by a fission process from the excited singlet. The time and magnetic field dependence of the triplet exciton decay indicate that the triplet exciton decay in the red phase occurs by diffusive bimolecular fusion, but in the yellow phase the triplet exciton decay is nondiffusive. We postulate that the unimolecular decay of the triplet exciton in the yellow phase results from exciton pinning by conformational disorder.