Cavity Catalysis by Cooperative Vibrational Strong Coupling of Reactant and Solvent Molecules. Issue 31 (4th July 2019)

• Record Type: Journal Article
• Authors: Lather, Jyoti; Bhatt, Pooja; Thomas, Anoop; Ebbesen, Thomas W.; George, Jino
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 31(2019)
• Page Start: 10635
• Page End: 10638
• Publication Date: 2019-07-04
• Subjects: cavity catalysis -- cooperativity -- polaritonic chemistry -- vibrational strong coupling; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201905407
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Here, we report the catalytic effect of vibrational strong coupling (VSC) on the solvolysis of para ‐nitrophenyl acetate (PNPA), which increases the reaction rate by an order of magnitude. This is observed when the microfluidic Fabry–Perot cavity in which the VSC is generated is tuned to the C=O vibrational stretching mode of both the reactant and solvent molecules. Thermodynamic experiments confirm the catalytic nature of VSC in the system. The change in the reaction rate follows an exponential relation with respect to the coupling strength of the solvent, indicating a cooperative effect between the solvent molecules and the reactant. Furthermore, the study of the solvent kinetic isotope effect clearly shows that the vibrational overlap of the C=O vibrational bands of the reactant and the strongly coupled solvent molecules is critical for the catalysis in this reaction. The combination of cooperative effects and cavity catalysis confirms the potential of VSC as a new frontier in chemistry. Abstract : This cavity doesn′t hurt : The solvolysis reaction of para ‐nitrophenyl acetate is accelerated by an order of magnitude through cooperative vibrational strong coupling of the reactant and solvent molecules at room temperature. The reaction mixture is injected into a Fabry–Perot (FP) cavity and the cavity mode is tuned to the carbonyl stretching mode of both the reactant and solvent molecules together to achieve strong coupling.