Pulse Radiolysis of TIPS-Pentacene and a Fluorene-bridged Bis(pentacene): Evidence for Intramolecular Singlet-Exciton Fission.

Exposing TIPS-pentacene in deaerated benzene to ionizing radiation generates a mixture of singlet- and triplet-excited states of the solute. The singlet undergoes radiative decay without spin conversion whereas the triplet undergoes radiationless decay on the microsecond time scale. The concentration of each species was established by dosimetry. The excited-singlet state is not observed on the nanosecond-time scale for a related fluorene-bridged bis(pentacene), but the triplet is present in high concentration. Failure to detect the excited-singlet state is attributed to fast intramolecular singlet-exciton fission (iSEF) which is found to produce two triplet species. A short-lived intermediate (τT = 145 ns) is identified as the species (T_T) having both pentacene units present as triplet states. The second transient is longer lived (τT = 7.5 μs) and is assigned to the corresponding species (T_G) with a single pentacene promoted to the triplet level. Dosimetry is used to conclude that iSEF partitions overwhelmingly in favor of T_G (70%) relative to T_T (25%). The total triplet yield from iSEF, therefore, is ca. 120% in this system, where the pentacene terminals are weakly coupled.