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Autotuning of Vibrational Strong Coupling for Site-Selective Reactions |
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| Authors: | Prof?Dr Kenji Hirai Hiroto Ishikawa Prof?Dr Yasufumi Takahashi Dr James A Hutchison Prof?Dr Hiroshi Uji-i |
| Institution: | 1. Division of Photonics and Optical Science, Research Institute for Electronic Science (RIES), Hokkaido University, North 20 West 10, Kita ward, Sapporo, Hokkaido, 001-0020 Japan;2. Division of Information Science and Technology, Graduate School of Information Science and Technology, Hokkaido University, North 14 West 9, Kita ward, Sapporo, Hokkaido, Japan;3. Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012 Japan
Graduate School of Engineering Electronics, Nagoya University Furocho, Chikusa-ku, Nagoya-shi, Aichi, 464-8603 Japan;4. School of Chemistry and ARC Centre of Excellence in Exciton Science, The University of Melbourne, Masson Rd, Parkville, VIC 3052 Australia;5. Division of Photonics and Optical Science, Research Institute for Electronic Science (RIES), Hokkaido University, North 20 West 10, Kita ward, Sapporo, Hokkaido, 001-0020 Japan Division of Information Science and Technology, Graduate School of Information Science and Technology, Hokkaido University, North 14 West 9, Kita ward, Sapporo, Hokkaido, Japan Department of Chemistry, KU Leuven, Celestijnenlaan 200F, 3001 Heverlee Leuven, Belgium Institute for Integrated Cell-Material Science (WPI-iCeMS), Kyoto University, Yohida Sakyo-ku, 606-8501 Kyoto, Japan |
| Abstract: | Site-selective chemistry opens new paths for the synthesis of technologically important molecules. When a reactant is placed inside a Fabry–Perot (FP) cavity, energy exchange between molecular vibrations and resonant cavity photons results in vibrational strong coupling (VSC). VSC has recently been implicated in modified chemical reactivity at specific reactive sites. However, as a reaction proceeds inside an FP cavity, the refractive index of the reaction solution changes, detuning the cavity mode away from the vibrational mode and weakening the VSC effect. Here we overcome this issue, developing actuatable FP cavities to allow automated tuning of cavity mode energy to maintain maximized VSC during a reaction. As an example, the site-selective reaction of the aldehyde over the ketone in 4-acetylbenzaldehyde is achieved by automated cavity tuning to maintain optimal VSC of the ketone carbonyl stretch during the reaction. A nearly 50 % improvement in site-selective reactivity is observed compared to an FP cavity with static mirrors, demonstrating the utility of actuatable FP cavities as microreactors for organic chemistry. |
| Keywords: | Fabry–Perot cavity prins reactions infrared spectroscopy piezoelectric actuators vibrational strong coupling |