Perylene-Monoimides: Singlet Fission Down-Conversion Competes with Up-Conversion by Geminate Triplet–Triplet Recombination

Abstract

Triplet-excited-state energies of perylene-monoimides (PMIs) lie in the range 1.12 eV ± 2 meV when compared to singlet-excited-state energies of about 2.39 eV ± 2 meV; therefore, the corresponding naphthalene-linked PMI-Dimer was investigated as a novel singlet-fission (SF) material. Ultrafast transient absorption measurements demonstrated the (S1S0)-to-1 (T1T1) trans formation and the involvement of a mediating step in the overall 1 (T1T1) formation. The intermediate is a charge-transfer state that links the initial (S1S0) with the final 1 (T1T1), and imposes charge-transfer character on both, which are thus denoted (S1S0)CT and 1 (T1T1)CT. At room temperature, the decorrelation and stability of 1 (T1T1)CT is affected by the geminate triplet−triplet recombination (G TTR) of the two triplets. Independent confirmation for G-TTR to afford up converted (S1S0)UC in fsTA and nsTA measurements with PMI-Dimer, came from probing PMI-Monomer (T1)s in triplet−triplet annihilation up-conversion (TTA UC). The G-TTR channel, active in the PMI-Dimer at room temperature, is suppressed by working at either low temperatures (∼140 K) or in polar solvents (benzonitrile): Both scenarios assist in stabilizing (T1T1)CT. As a consequence, the triplet quantum yields are 4.2% and 14.9% at room temperature and 140 K, respectively, in 2-methyltetrahydrofuran.