Sreelakshmi, PA and Mahashaya, R and Leitherer, S and Rashid, U and Hamill, JM and Nair, M and Rajamalli, P and Kaliginedi, V (2024) Electric Field-Induced Sequential Prototropic Tautomerism in Enzyme-like Nanopocket Created by Single Molecular Break Junction. In: Journal of the American Chemical Society .
|
PDF
Jou_Ame_Che_Soc_2024.pdf - Published Version Download (6MB) | Preview |
|
|
PDF
Jou_Ame_Che_Soc_2024_Sup.pdf - Published Supplemental Material Download (20MB) | Preview |
Abstract
Mastering the control of external stimuli-induced chemical transformations with detailed insights into the mechanistic pathway is the key for developing efficient synthetic strategies and designing functional molecular systems. Enzymes, the most potent biological catalysts, efficiently utilize their built-in electric field to catalyze and control complex chemical reactions within the active site. Herein, we have demonstrated the interfacial electric field-induced prototropic tautomerization reaction in acylhydrazone entities by creating an enzymatic-like nanopocket within the atomically sharp gold electrodes using a mechanically controlled break junction (MCBJ) technique. In addition to that, the molecular system used here contains two coupled acylhydrazone reaction centers, hence demonstrating a cooperative stepwise electric field-induced reaction realized at the single molecular level. Furthermore, the mechanistic studies revealed a proton relay-assisted tautomerization showing the importance of external factors such as solvent in such electric field-driven reactions. Finally, single-molecule charge transport and energetics calculations of different molecular species at various applied electric fields using a polarizable continuum solvent model confirm and support our experimental findings. Thus, this study demonstrates that mimicking an enzymatic pocket using a single molecular junction�s interfacial electric field as a trigger for chemical reactions can open new avenues to the field of synthetic chemistry. © 2024 The Authors. Published by American Chemical Society.
| Item Type: | Journal Article |
|---|---|
| Publication: | Journal of the American Chemical Society |
| Publisher: | American Chemical Society |
| Additional Information: | The copyright for this article belongs to author. |
| Keywords: | Addition reactions; Phase diagrams; Surface discharges; Synthesis (chemical), Break-junctions; Chemical transformations; Electric field induced; External stimulus; Mechanistic pathways; Molecular systems; Nanopockets; Prototropic tautomerisms; Synthetic strategies; Tautomerizations, Charge transfer |
| Department/Centre: | Division of Chemical Sciences > Inorganic & Physical Chemistry Division of Chemical Sciences > Materials Research Centre |
| Date Deposited: | 26 Nov 2024 12:17 |
| Last Modified: | 26 Nov 2024 12:17 |
| URI: | http://eprints.iisc.ac.in/id/eprint/86918 |
Actions (login required)
 |
View Item |
