The harvesting of 'hot' triplet excitons through high-lying reverse intersystem crossing mechanism has emerged as a hot research issue in the field of organic light-emitting diodes. However, if high-lying reverse intersystem crossing materials lack the capability to convert 'cold' T1 excitons into singlet ones, the actual maximum exciton utilization efficiency would generally deviate from 100%. Herein, through comparative studies on two naphthalimide-based compounds CzNI and TPANI, we revealed that the 'cold' T1 excitons in high-lying reverse intersystem crossing materials can be utilized effectively through the triplet-triplet annihilation-mediated high-lying reverse intersystem crossing process if they possess certain triplet-triplet upconversion capability. Especially, quite effective triplet-triplet annihilation-mediated high-lying reverse intersystem crossing can be triggered by endowing the high-lying reverse intersystem crossing process with a 3ππ*→1nπ* character. By taking advantage of the permanent orthogonal orbital transition effect of 3ππ*→1nπ*, spin-orbit coupling matrix elements of ca. 10 cm-1 can be acquired, and hence ultra-fast mediated high-lying reverse intersystem crossing process with rate constant over 109 s-1 can be realized.
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