Journal of the American Chemical Society, vol. 136, issue 20 (2014) pp. 7363-7373 Published by American Chemical Society
In order to elucidate the mechanism of singlet fission in thin films of 1,3-diphenylisobenzofuran (1) we have performed ultrafast transient absorption spectroscopy as a function of sample temperature and excitation fluence on polycrystalline thin films composed of two polymorphs. Our earlier investigations revealed that films enriched in a particular polymorph of 1 displayed near 200% efficiency for triplet formation at 77 K, while films composed primarily of a second polymorph had a very low triplet quantum yield. Present data confirm the triplet yield disparities in the two polymorphs and demonstrate the distinct fates of the initially prepared singlets in films of different structure. Singlet fission is inhibited in the more stable polymorph due to rapid excimer formation and trapping. The less stable polymorph undergoes highly efficient singlet fission with a dominant time constant of 10-30 ps and without strong thermal activation. Transient absorption measurements with varying excitation fluence indicate that singlet-singlet annihilation is a primary competitor of singlet fission at higher fluence and that fission from higher-lying states can also contribute to the triplet formation process. Measurements employing different excitation energies and sample temperatures reveal the role that trapping processes play in attenuating the triplet quantum yield to produce the complex temperature dependence of the singlet fission yield. The rate constants for singlet fission itself are essentially temperature independent.
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