High-Level Reverse Intersystem Crossing and Molecular Rigidity Improve Spin Statistics for Triplet-Triplet...

The structural factors affecting triplet-triplet annihilation (TTA) at the molecular level are not well-understood. Here, our steady-state photoluminescence and transient absorption results demonstrate that the spin statistical factor, η, decreases from 0.60 to 0.46 and 0.14 going from 9,10-diphenylanthracene (DPA) to the 1,5-DPA and 2,6-DPA isomers, respectively, during photon upconversion with a platinum octaethylporphyrin sensitizer. Density functional theory (DFT) shows that η depends on the energetics of hot triplet states and molecular rigidity. The significantly high conical intersection energy between the S₀ and T₁ states for 9,10-DPA gives its longer triplet lifetime. Time-dependent DFT calculations show that 9,10-DPA and 1,5-DPA can undergo high-level reverse intersystem crossing from their T₂ and T₃ states, respectively, to the bright S₁ state, increasing the limit of the spin statistical factor. Both factors ultimately serve to enhance the TTA efficiency. This work provides insight into designing molecules for efficient light-emitting and photon upconversion applications.