Validation of the CoGEF Method as a Predictive Tool for Polymer Mechanochemistry

Area of Science:

• Polymer Chemistry
• Materials Science
• Computational Chemistry

Background:

• Mechanophores are crucial for developing advanced polymers with applications in sensing, molecular release, and self-healing materials.
• Understanding structure-activity relationships is key for designing effective mechanophores, but experimental limitations necessitate computational approaches.
• The constrained geometries simulate external force (CoGEF) method offers an accessible way to predict molecular response to mechanical force.

Purpose of the Study:

• To systematically evaluate all reported covalent mechanophores using the CoGEF method.
• To compare computational predictions of mechanochemical reactivity with experimental data.
• To validate the CoGEF method as a reliable tool for guiding mechanophore design.

Main Methods:

• Utilized the constrained geometries simulate external force (CoGEF) method to simulate mechanical force on molecules.
• Performed density functional theory calculations at the B3LYP/6-31G* level.
• Evaluated over 100 covalent mechanophores and included inactive molecules as negative controls.

Main Results:

• CoGEF predictions showed excellent agreement with experimental results for mechanochemical reactivity.
• Calculated bond rupture forces from CoGEF reliably indicated mechanochemical activity.
• The study provides a comprehensive catalog of over 100 mechanophores.

Conclusions:

• The CoGEF method is validated as a powerful and reliable tool for predicting mechanochemical reactivity.
• Widespread adoption of CoGEF will accelerate the development of polymer mechanochemistry.
• This work facilitates the rational design of novel mechanophores for diverse applications.