Korean Journal of Chemical Engineering

, Volume 36, Issue 11, pp 1791–1798 | Cite as

Visible-to-UV triplet-triplet annihilation upconversion from a thermally activated delayed fluorescence/pyrene pair in an air-saturated solution

  • Hak-Lae Lee
  • Myung-Soo Lee
  • Hyun Park
  • Won-Sik Han
  • Jae-Hyuk KimEmail author
Rapid Communication


Despite increasing use of triplet-triplet annihilation upconversion (TTA-UC) of low-energy visible light, the generation of ultraviolet (UV) photons by TTA remains challenging because of the difficulty in finding sensitizers and acceptors with suitable energy levels. Here, we report efficient, photostable visible-to-UV TTA-UC in an air-saturated solution using a new pair with suitable energy levels: a thermally activated delayed fluorescence (TADF) molecule and pyrene. 4CzIPN, which has extremely small energy difference ΔEST (0.083 eV), was used as the TADF sensitizer to promote effective triplet energy transfer to the acceptor. When oleic acid was used as an effective singlet oxygen receptor in an air-saturated solution, the 4CzIPN/pyrene pair exhibited bright upconverted emission at 370–430 nm under 445 nm laser excitation, but no noticeable upconverted emission was observed when 4CzIPN was paired with previously reported UV-emitting acceptors [2,5-diphenyloxazole (PPO), p-terphenyl, and p-quaterphenyl]. TTA was confirmed by the quadratic dependence of the upconverted emission intensity on the 445 nm laser power density. The maximum quantum yield of the upconverted emission from the 4CzIPN/pyrene pair was 0.66%, which is considerable when compared with that of a previously reported visible-to-UV TTA-UC system with a biacetyl/PPO pair (0.58%).


Upconversion Triplet-Triplet Annihilation Anti-Stokes Emission UV Generation Thermally Activated Delayed Fluorescence 





energy difference between S1 and T1 states


integrated fluorescence intensity


refractive index of solvent


quantum yield


TTA-UC efficiency


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This work; was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2018R1D1A3B07049650) and by the Korean government (MSIT) through GCRC-SOP (No. 2011-0030013).


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Copyright information

© The Korean Institute of Chemical Engineers 2019

Authors and Affiliations

  • Hak-Lae Lee
    • 1
  • Myung-Soo Lee
    • 1
  • Hyun Park
    • 2
  • Won-Sik Han
    • 3
  • Jae-Hyuk Kim
    • 1
    Email author
  1. 1.Department of Chemical and Environmental EngineeringPusan National UniversityBusanKorea
  2. 2.Naval Architecture & Ocean EngineeringPusan National UniversityBusanKorea
  3. 3.Department of ChemistrySeoul Women’s UniversitySeoulKorea

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