Visible‐to‐UV Photon Upconversion in Nanostructured Chromophoric Ionic Liquids

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  • Shota Hisamitsu
    Department of Chemistry and Biochemistry, Graduate School of Engineering, Center for Molecular Systems (CMS) Kyushu University 744 Moto-oka, Nishi-ku Fukuoka 819-0395 Japan
  • Junji Miyano
    Department of Chemistry and Biochemistry, Graduate School of Engineering, Center for Molecular Systems (CMS) Kyushu University 744 Moto-oka, Nishi-ku Fukuoka 819-0395 Japan
  • Keisuke Okumura
    Department of Chemistry and Biochemistry, Graduate School of Engineering, Center for Molecular Systems (CMS) Kyushu University 744 Moto-oka, Nishi-ku Fukuoka 819-0395 Japan
  • Joseph Ka‐Ho Hui
    Department of Chemistry and Biochemistry, Graduate School of Engineering, Center for Molecular Systems (CMS) Kyushu University 744 Moto-oka, Nishi-ku Fukuoka 819-0395 Japan
  • Nobuhiro Yanai
    Department of Chemistry and Biochemistry, Graduate School of Engineering, Center for Molecular Systems (CMS) Kyushu University 744 Moto-oka, Nishi-ku Fukuoka 819-0395 Japan
  • Nobuo Kimizuka
    Department of Chemistry and Biochemistry, Graduate School of Engineering, Center for Molecular Systems (CMS) Kyushu University 744 Moto-oka, Nishi-ku Fukuoka 819-0395 Japan

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<jats:title>Abstract</jats:title><jats:p>Visible‐to‐ultraviolet (vis‐to‐UV) triplet‐triplet annihilation based photon upconversion (TTA‐UC) is achieved in a non‐volatile chromophoric ionic liquid (IL) for the first time. A novel IL is synthesized by combining UV‐emitting anion 4‐(2‐phenyloxazol‐5‐yl)benzenesulfonate (PPOS) and trihexyltetradecylphosphonium cation (P<jats:sub>66614</jats:sub>). The nanostructured organization of chromophoric anions is demonstrated by synchrotron X‐ray and optical measurements. When the IL is doped with a triplet sensitizer tris(2‐phenylpyridinato)iridium(III) (Ir(ppy)<jats:sub>3</jats:sub>), the visible‐to‐UV TTA‐UC with a relatively low threshold excitation intensity of 61 mW cm<jats:sup>−2</jats:sup> is achieved. This is due to a large triplet diffusion coefficient in the IL (1.4×10<jats:sup>−7</jats:sup> cm<jats:sup>2</jats:sup> s<jats:sup>−1</jats:sup>) as well as a high absorption coefficient 15 cm<jats:sup>−1</jats:sup> and a long PPOS triplet lifetime of 1.55 ms, all implemented in the condensed IL system. This work demonstrates the unique potential of ILs to control chromophore arrangements for desired functions.</jats:p>

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