Quintet-triplet mixing determines the fate of the multiexciton state produced by singlet fission in a terrylenediimide dimer at room temperature.

ABSTRACT: Singlet fission (SF) is a photophysical process in which one of two adjacent organic molecules absorbs a single photon, resulting in rapid formation of a correlated triplet pair (T₁T₁) state whose spin dynamics influence the successful generation of uncorrelated triplets (T₁). Femtosecond transient visible and near-infrared absorption spectroscopy of a linear terrylene-3,4:11,12-bis(dicarboximide) dimer (TDI₂), in which the two TDI molecules are directly linked at one of their imide positions, reveals ultrafast formation of the (T₁T₁) state. The spin dynamics of the (T₁T₁) state and the processes leading to uncoupled triplets (T₁) were studied at room temperature for TDI₂ aligned in 4-cyano-4'-pentylbiphenyl (5CB), a nematic liquid crystal. Time-resolved electron paramagnetic resonance spectroscopy shows that the (T₁T₁) state has mixed ⁵(T₁T₁) and ³(T₁T₁) character at room temperature. This mixing is magnetic field dependent, resulting in a maximum triplet yield at ?200 mT. The accessibility of the ³(T₁T₁) state opens a pathway for triplet-triplet annihilation that produces a single uncorrelated T₁ state. The presence of the ⁵(T₁T₁) state at room temperature and its relationship with the ¹(T₁T₁) and ³(T₁T₁) states emphasize that understanding the relationship among different (T₁T₁) spin states is critical for ensuring high-yield T₁ formation from singlet fission.

SUBMITTER: Chen M 

PROVIDER: S-EPMC6486782 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature