Using oriented external electric fields to manipulate rupture forces of mechanophores

Scheele, Tarek; Neudecker, Tim

doi:10.1039/d3cp03965j

Cited by 2 publications

(1 citation statement)

References 50 publications

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“…Recently, Scheele and Neudecker have reported the breakage of the scissile bonds under OEEF. 30 Using various classes of mechanophores, we have shown that the OEEF significantly augments mechanochemistry.…”

Section: ■ Introductionmentioning

confidence: 98%

Oriented External Electric Field Controls the Rupture Forces in Mechanophores

Das,

Datta

2024

J. Phys. Chem. B

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Controlling the reactivity of molecules under a mechanical pull has generated significant interest in organic and polymer chemistry. Inducing mechano-lability for otherwise rigid molecules has been possible through structural alterations like adjusting the pulling group, ring strain, and electron density of the scissile bond. In this article, we report that an oriented external electric field (OEEF) can significantly assist in mechanochemical transformations. Using a structurally diverse set of ring-opening reactions, 1(a)−4(a), we show that the critical force required for bond-cleavage, F rup , gets appreciably reduced when the OEEF acts in-phase with the bond-polarity direction. The primary condition for utilizing OEEF along with mechanochemistry is the requirement of structural asymmetry along the target bond. Effectively therefore, any polar ring-opening reaction might be manipulated by OEEF. The versatility of the strategy of using OEEF and mechanical force together can also be appreciated by the enhanced rupture force when the direction of the OEEF is flipped. We show that mechanical pulling and electric field can act as entwined twins toward mechano-lability.

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Section: ■ Introductionmentioning

confidence: 98%

Oriented External Electric Field Controls the Rupture Forces in Mechanophores

Das,

Datta

2024

J. Phys. Chem. B

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On the Interplay Between Force, Temperature, and Electric Fields in the Rupture Process of Mechanophores

Scheele,

Neudecker

2024

ChemPhysChem

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The use of oriented external electric fields (OEEFs) shows promise as an alternative approach to chemical catalysis. The ability to target a specific bond by aligning it with a bond‐weakening electric field may be beneficial in mechanochemical reactions, which use mechanical force to selectively rupture bonds. Previous computational studies have focused on a static description of molecules in OEEFs, neglecting to test the influence of thermal oscillations on molecular stability. Here, we performed ab initio molecular dynamics (AIMD) simulations based on density functional theory (DFT) to investigate the behaviour of a model mechanophore under the simultaneous influence of thermal and electric field effects. We show that the change in bond length caused by a strong electric field is largely independent of the temperature, both without and with mechanical stretching forces applied to the molecule. The amplitude of thermal oscillations increases with increasing field strength and temperature, but at low temperatures, the application of mechanical force leads to an additional increase in amplitude. Our research shows that methods for applying mechanical force and OEEFs can be safely combined and included in an AIMD simulation at both low and high temperatures, allowing researchers to computationally investigate mechanochemical reactions in realistic application scenarios.

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Using oriented external electric fields to manipulate rupture forces of mechanophores

Abstract: Using electronic structure calculations, we show that oriented external electric fields have a strong effect on the mechanical force required to activate mechanophores.

Cited by 2 publications

References 50 publications

Oriented External Electric Field Controls the Rupture Forces in Mechanophores

Oriented External Electric Field Controls the Rupture Forces in Mechanophores

On the Interplay Between Force, Temperature, and Electric Fields in the Rupture Process of Mechanophores

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