Oriented electric fields as future smart reagents in chemistry

Abstract

Oriented external electric fields (OEEFs) as 'smart reagents' are no longer a theoretical dream. Here, we discuss the wide-ranging potential of using OEEFs to catalyse and control a variety of non-redox reactions and impart selectivity at will. An OEEF along the direction of electron reorganization (the so-called reaction axis) will catalyse nonpolar reactions by orders of magnitude, control regioselectivity and induce spin-state selectivity. Simply flipping the direction of the OEEF or orienting it off of the reaction axis, will control at will the endo/exo ratio in Diels-Alder reactions and steps in enzymatic cycles. This Perspective highlights these outcomes using theoretical results for hydrogen abstraction reactions, epoxidation of double bonds, C-C bond forming reactions, proton transfers and the cycle of the enzyme cytochrome P450, as well as recent experimental data. We postulate that, as experimental techniques mature, chemical syntheses may become an exercise in zapping oriented molecules with OEEFs.

Molecular Semiconductors for Logic Operations: Dead‐End or Bright Future?

“…Several authors have reported the use of electric fields on the order of E ≈ 10 10 V m −1 , routinely reached with scanning tunneling microscopes, to control a variety of nonredox reactions . This emerging research line has recently been reviewed . Besides, classical redox chemistry applies with the known electrochemical window, i.e., the voltage range in which a substance is neither oxidized nor reduced, that is generally not greater than a few volts around Fc/Fc+ electrodes for most organic solvents and ionic liquids .…”

TITAN: A Code for Modeling and Generating Electric Fields—Features and Applications to Enzymatic Reactivity

“…Often times, it is more meaningful to consider the projection of an electric field in one specific direction. As mentioned before, the exact orientation of the electric field—and its alignment with the considered bond or reaction axis—is of paramount importance to gauge its impact on the chemical reactivity. One can define the oriented electric field (OEF), , at point O ( a , b , c ) in a given direction as follows: …”

“…In recent years, (external) electric fields are increasingly being recognized as potent—and smart—effectors of chemical change . Their introduction in the toolbox of synthetic chemists could potentially be a game changer, opening new (and more sustainable) routes toward chemical synthesis .…”

“…The seemingly endless potential of electric fields as a means for the control of chemical reactivity has sparked a lot of interest, not only from the biochemistry community, but also from organic chemists, as well as others . As a consequence, there is an increasing need for computational and theoretical chemists to extend their activities and expertise to this new research field.…”

A greener catalyst for hydroboration of imines—external electric field modify the reaction mechanism

“…Up to now, some endeavors had been done to develop a new methodology in accordance with green chemistry principles . An emerging greener catalyst is coming into one's sight, which is the external electric field (EEF), as a smart reagent to catalyze reactions had been reported by theory and experiment . Especially, the experiment of EEF by Aragonés et al paved the way for the development of EEF in catalyzing chemistry reactions.…”