| Autor: |
Sreelakshmi PA; Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012, India., Mahashaya R; Materials Research Centre, Indian Institute of Science, Bangalore 560012, India., Leitherer S; Department of Chemistry and Nano-Science Center, University of Copenhagen, Universitetsparken 5, DK- 2100 Copenhagen Ø, Denmark., Rashid U; Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012, India., Hamill JM; Department of Chemistry and Nano-Science Center, University of Copenhagen, Universitetsparken 5, DK- 2100 Copenhagen Ø, Denmark., Nair M; Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012, India., Rajamalli P; Materials Research Centre, Indian Institute of Science, Bangalore 560012, India., Kaliginedi V; Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012, India. |
| Abstrakt: |
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. |
