Enhancing the Statistical Probability Factor in Triplet-Triplet Annihiltaion Photon Upconversion via TIPS Functionalization

Abstract

We investigated the influence of triisopropylsilyl (TIPS) functionalization on annihilators in triplet-triplet annihilation photon upconversion, specifically focusing on their spin statistical probability factor. A new green-emitting annihilator 3,9-bis((triisopropylsilyl)ethynyl)perylene (TIPS-PY) displaying a record red-to-green TTA-UC quantum yield of 13.7% (50% theoretical maximum) is synthesized. This remarkable efficiency was achieved due to the following features of the TIPS functionalization of PY: 1) retaining a high fluorescence quantum yield of 95%, 2) reduced triplet energy to 1.29 eV enabling efficient triplet energy transfer (~100%) from the sensitizer, PdTPBP (T1= 1.55 eV), and 3) a high efficiency of singlet generation after triplet coupling, indicated by the statistical probability factor, f = 39.2% ± 2.4%. Notably, the f value of TIPS-PY surpasses other annihilators in the 470-570 nm emission range. Excited state computational analysis using TheoDORE, revealed a higher percentage of charge transfer character in S0S1 in TIPS-PY compared to PY, indicative of higher singlet-like character in their triplet-pair state 1(T1T1), which can enhance the coupling of the triplet-pair state with the excited singlet-state, thereby increasing the efficiency of singlet generation, a phenomenon undisclosed before. Furthermore, the suitable T1 of TIPS-PY enables upconversion of 730 nm light when sensitized with Os(m-peptpy)2(TFSI)2 (T1 = 1.63 eV), demonstrating the broad upconversion range of TIPS-PY in the phototherapeutic window desired for biological applications.