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Supramolecular Crowding Can Avoid Oxygen Quenching of Photon Upconversion in Water
Authors:Hironori Kouno  Yoichi Sasaki  Prof Nobuhiro Yanai  Prof Nobuo Kimizuka
Institution: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
Abstract:A common challenge in chemistry that deals with photoexcited states is to avoid oxygen quenching. This is crucial for hot research fields such as photon upconversion (UC), in which oxygen-sensitive triplet excited states play pivotal roles. However, methods to avoid oxygen quenching in aqueous media are far more limited despite eagerly anticipated catalytic and biological applications. This work introduces a simple strategy to achieve air-stable triplet–triplet annihilation (TTA)-based UC in water, namely, supramolecular crowding. Amphiphilic cationic acceptor molecules and anions with long alkyl chains co-assemble in water in which hydrophobic donor molecules are molecularly dispersed. Despite the common notion that oxygen molecules diffuse readily across hydrophobic domains in water, more than 80 % of the TTA-UC emission of the obtained hydrophobic co-assemblies is maintained in air-saturated water. This work demonstrates the new promising potential of supramolecular chemistry for photophysical and photochemical functions with oxygen-sensitive species.
Keywords:photochemistry  photon upconversion  steric hindrance  supramolecular chemistry  triplet–triplet annihilation
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