Temperature Tuning of Coherent Mixing between States Driving Singlet Fission in a Spiro-Fused Terrylenediimide Dimer

The excited-state dynamics of a spiro-fused terrylene-3,4:11,12-bis(dicarboximide) (TDI) dimer (sTDI) in toluene and 2-methyltetrahydrofuran (mTHF) were investigated as a function of temperature using femtosecond- and nanosecond-transient absorption spectroscopy, as well as two-dimensional electronic spectroscopy. The spiro conjugation and the corresponding geometry of this compound guarantee a short intermonomer distance along with a partial orbital overlap between the orthogonal TDI π-electron systems, providing electronic coupling between the TDIs. Photoexcitation of sTDI in toluene, a low dielectric solvent, at 295 K, results in the ultrafast formation of a state composed of a coherent mixture of singlet ¹(S₁S₀), multiexciton ¹(T₁T₁), and charge-transfer (CT) electronic characters. This mixed species decays to decorrelated triplet states on the nanosecond timescale, completing the process of intramolecular singlet fission (SF) in sTDI. Upon decreasing the temperature from 295 to 200 K, the contribution of the ¹(T₁T₁) state to the mixed species decreases concurrently with an increase in the CT state character. We attribute this behavior to the variation in the vibrational energy level alignment between the states comprising the mixture due to changes in the temperature and hence the local dielectric environment. In contrast, photoexcitation of sTDI in more polar mTHF at 295 K results in the formation of a mixed singlet and CT state before undergoing symmetry-breaking charge separation, owing to the increased stabilization of the CT state in the medium. However, in glassy mTHF at 85 K, photoexcited sTDI exhibits discernible multiexciton character, comparable to that observed in toluene at 200 K, which we rationalize by the similarity of the dielectric constants under these two sets of conditions. These observations of mixed states of varying diabatic contributions over the range of experimental conditions show that the temperature and the static dielectric constant can directly control the composition of the electronically mixed excited state of sTDI and thus the fate of the SF process.