利用TIPS功能化提高三重-三重湮灭光子上转换的统计概率因子

IF 7.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science Pub Date : 2025-10-07 DOI:10.1039/d5sc05248c

Lukas Naimovicius, Manvydas Dapkevičius, Edvinas Radiunas, Mila Miroshnichenko, Gediminas Kreiza, Carles Alcaide, Paulius Baronas, Yoichi Sasaki, Nobuhiro Yanai, Nobuo Kimizuka, Andrew Brian Pun, Miquel Solà, Pankaj Bharmoria, Karolis Kazlauskas, Kasper Moth-Poulsen

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引用次数: 0

摘要

研究了三异丙基硅基（TIPS）功能化对三重态-三重态湮灭光子上转换中湮灭子的影响，特别关注了它们的自旋统计概率因子。合成了一种新的绿色发射湮灭体3,9-双（（三异丙基硅基）乙基）苝（TIPS-PY），其红绿TTA-UC量子产率达到创纪录的13.7%（理论最大值为50%）。这一显著的效率是由于PY的TIPS功能化的以下特点：1)保持了95%的高荧光量子产率，2)将三重态能量降低到1.29 eV，实现了从敏化剂PdTPBP （T1= 1.55 eV）高效的三重态能量传递（~100%），3)三重态耦合后单线态生成的效率很高，统计概率因子f = 39.2%±2.4%。值得注意的是，TIPS-PY在470 ~ 570nm发射范围内的f值超过了其他湮灭子。利用TheoDORE进行激发态计算分析发现，TIPS-PY中S0S1的电荷转移特征比PY高，这表明它们的三重态1（T1T1）具有更高的单重态特征，这可以增强三重态与激发态的耦合，从而提高单重态产生的效率，这是以前未发现的现象。此外，TIPS-PY合适的T1可以在Os(m-peptpy)2(TFSI)2 （T1 = 1.63 eV）敏化时实现730nm光的上转换，这表明TIPS-PY在生物应用所需的光疗窗口中具有较宽的上转换范围。

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

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.

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来源期刊

Chemical Science CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

4.80%

发文量

1352

审稿时长

2.1 months

期刊介绍： Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.