Cavity Catalysis by Cooperative Vibrational Strong Coupling of Reactant and Solvent Molecules1. (3rd July 2019)

• Record Type: Journal Article
• Authors: Lather, Jyoti; Bhatt, Pooja; Thomas, Anoop; Ebbesen, Thomas W.; George, Jino
• Is Part Of: Angewandte Chemie. Volume 131:Number 31(2019)
• Page Start: 10745
• Page End: 10748
• Publication Date: 2019-07-03
• Subjects: Kavitätskatalyse -- Kooperativität -- Polaritonische Chemie -- Starke Schwingungskopplung; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201905407
• Languages: English
• ISSNs: 0044-8249

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 : Gekoppelt und beschleunigt : Die Solvolysereaktion von para ‐Nitrophenylacetat wird durch kooperative starke Schwingungskopplung zwischen Reaktant und Lösungsmittel bei Raumtemperatur um eine Größenordnung beschleunigt. Die Reaktionsmischung wird dabei in eine Fabry‐Perot(FP)‐Kavität injiziert und die starke Kopplung durch Abstimmung der Kavitätsmode auf die Carbonyl‐Streckschwingung von sowohl Reaktant als auch Lösungsmittelmolekülen erreicht.