Title Enhancing the statistical probability factor in triplet–triplet annihilation photon upconversion via TIPS functionalization
Authors Naimovičius, Lukas ; Dapkevičius, Manvydas ; Radiunas, Edvinas ; Miroshnichenko, Mila ; Kreiza, Gediminas ; Alcaide, Carles ; Baronas, Paulius ; Sasaki, Yoichi ; Yanai, Nobuhiro ; Kimizuka, Nobuo ; Pun, Andrew B ; Solà, Miquel ; Bharmoria, Pankaj ; Kazlauskas, Karolis ; Moth-Poulsen, Kasper
DOI 10.1039/D5SC05248C
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Is Part of Chemical science.. Cambridge : Royal Society of Chemistry (RSC). 2025, vol. 16, iss. 43, p. 20255-20264.. ISSN 2041-6520. eISSN 2041-6539
Abstract [eng] 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) was 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 (T 1 = 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 S 0 S 1 in TIPS-PY compared to PY, indicative of higher singlet-like character in their triplet-pair state 1 (T 1 T 1 ), 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 T 1 of TIPS-PY enables upconversion of 730 nm light when sensitized with Os(m-peptpy)2(TFSI)2 (T 1 = 1.63 eV), demonstrating the broad upconversion range of TIPS-PY in the phototherapeutic window desired for biological applications.
Published Cambridge : Royal Society of Chemistry (RSC)
Type Journal article
Language English
Publication date 2025
CC license CC license description