Lather Jyoti, Bhatt Pooja, Thomas Anoop, Ebbesen Thomas W, George Jino
Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER), Mohali, Punjab-, 140306, India.
University of Strasbourg, CNRS, ISIS & icFRC, 8 allée G. Monge, 67000, Strasbourg, France.
Angew Chem Int Ed Engl. 2019 Jul 29;58(31):10635-10638. doi: 10.1002/anie.201905407. Epub 2019 Jul 4.
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.
在此，我们报道了振动强耦合（VSC）对乙酸对硝基苯酯（PNPA）溶剂解的催化作用，其使反应速率提高了一个数量级。当产生VSC的微流控法布里 - 珀罗腔被调谐到反应物和溶剂分子的C = O振动拉伸模式时，会观察到这种情况。热力学实验证实了系统中VSC的催化性质。反应速率的变化与溶剂的耦合强度呈指数关系，表明溶剂分子与反应物之间存在协同效应。此外，对溶剂动力学同位素效应的研究清楚地表明，反应物的C = O振动带与强耦合溶剂分子的振动重叠对于该反应中的催化作用至关重要。协同效应和腔催化的结合证实了VSC作为化学新前沿的潜力。
