Modulating TTA efficiency through control of high energy triplet states

Abstract

An ideal annihilator in triplet–triplet annihilation photon upconversion (TTA-UC) can achieve a maximum of 50% quantum efficiency. This spin statistical limit depends on the energies of the triplet states of the annihilator molecule, with only 20% quantum efficiencies possible in less-optimal energy configurations (E_T2 ≤ 2E_T1). Our work utilises three perylene analogues substituted with phenyl in sequential positions. When substituted in the bay position the isomer displays drastically lowered upconversion yields, which can be explained by the system going from an ideal to less-ideal energy configuration. We further concluded position 2 is the best site when functionalising perylene without a wish to affect its photophysics, thus demonstrating how molecular design can influence upconversion quantum efficiencies by controlling the energetics of triplet states through substitution. This will in turn help in the design of molecules that maximise upconversion efficiencies for materials applications.