Singlet Fission as the Gateway to Triplet Generation in Heavy Atom-Free Organic Molecules

Triplet generations in heavy atom-free organic molecules are primarily revealed to proceed through singlet fissions (SFs) by investigating the contributions of SFs and intersystem crossings to the generation rates. The spin-flip long-range corrected time-dependent density functional theory calculations on 11 organic molecules known for triplet generation under photoirradiation are performed. The correlation between the descriptors for SF and the experimental singlet-to-triplet conversion rates strongly supports the predominance of SF progressions in all these molecules, corroborated by experimental observations of their triplet-triplet annihilations. Based on these findings, we propose updated conditions for SF progression: There is a high-absorption singlet state just above the triplet-triplet excitation of the chromophore dimer, or the singlet (triplet-triplet) excitation itself is responsible for photoabsorption. To the best of our knowledge, all organic molecules known for rapid triplet state generation fulfill these conditions.