Thermally modulated triplet-triplet annihilation: Deciphering the temperature dependence of upconversion dynamics

• Published in: The Journal of chemical physics Vol. 163; no. 6
• Main Authors: Shao, Jinsong, Zhang, Yiwei, Liu, Haoran, Duan, Doudou, Sun, Zhongfa, Lu, Zhou, Wei, Yaxiong, Xu, Xinsheng
• Format: Journal Article
• Language: English
• Published: United States 14.08.2025
• ISSN: 1089-7690
• DOI: 10.1063/5.0277862

The quantum efficiency ceiling of triplet-triplet annihilation upconversion is intrinsically governed by the spin statistical factor (f), yet the physical origin of its anomalously elevated values (f > 0.6) remains a subject of intense debate. By conducting systematic variable-temperature kinetic studies, integrating time-resolved transient absorption spectroscopy with steady-state fluorescence spectral analysis, we elucidated the temperature-dependent reaction dynamics of the benchmark PtOEP/DPA system to investigate the interaction between f and high-energy excited-state (T2) decay pathways. Notably, the positive temperature dependence of f (rising from 0.575 at 190 K to 0.808 at 280 K) and a small activation energy (Ea = 1.92 kJ/mol) demonstrated the dominance of a direct 3(AA)* → S1 reverse intersystem crossing (RISC) mechanism while excluding the hypothesized 3(AA)* → T2 → S1 cascade. These results not only resolve longstanding debates concerning f-enhancement but also provide a rationale for designing annihilators that exploit low-barrier RISC pathways to circumvent spin-statistical constraints.