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

Klein, Isabel M. and Husic, Corey C. and Kovács, Dávid P. and Choquette, Nicolas J. and Robb, Maxwell J. (2020) Validation of the CoGEF Method as a Predictive Tool for Polymer Mechanochemistry. Journal of the American Chemical Society, 142 (38). pp. 16364-16381. ISSN 0002-7863.

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The development of force-responsive molecules called mechanophores is a central component of the field of polymer mechanochemistry. Mechanophores enable the design and fabrication of polymers for a variety of applications ranging from sensing to molecular release and self-healing materials. Nevertheless, an insufficient understanding of structure–activity relationships limits experimental development, and thus computation is necessary to guide the structural design of mechanophores. The constrained geometries simulate external force (CoGEF) method is a highly accessible and straightforward computational technique that simulates the effect of mechanical force on a molecule and enables the prediction of mechanochemical reactivity. Here, we use the CoGEF method to systematically evaluate every covalent mechanophore reported to date and compare the predicted mechanochemical reactivity to experimental results. Molecules that are mechanochemically inactive are also studied as negative controls. In general, mechanochemical reactions predicted with the CoGEF method at the common B3LYP/6-31G* level of density functional theory are in excellent agreement with reactivity determined experimentally. Moreover, bond rupture forces obtained from CoGEF calculations are compared to experimentally measured forces and demonstrated to be reliable indicators of mechanochemical activity. This investigation validates the CoGEF method as a powerful tool for predicting mechanochemical reactivity, enabling its widespread adoption to support the developing field of polymer mechanochemistry. Secondarily, this study provides a contemporary catalog of over 100 mechanophores developed to date.

Item Type:Article
Related URLs:
URLURL TypeDescription
Husic, Corey C.0000-0003-0248-7484
Robb, Maxwell J.0000-0002-0528-9857
Additional Information:© 2020 American Chemical Society. Received: June 25, 2020; Published: September 9, 2020. Funding from Caltech and the Dow Next Generation Educator Fund is gratefully acknowledged. I.M.K. was supported by an NSF Graduate Research Fellowship (DGE-1745301). We also thank the Caltech-Cambridge Exchange Program (D.P.K.) and the Summer Undergraduate Research Fellowship Program at Caltech (N.J.C.) for financial support, and Stephen Craig for helpful discussion. Author Contributions. I.M.K. and C.C.H. contributed equally. The authors declare no competing financial interest.
Funding AgencyGrant Number
Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
Dow Next Generation Educator FundUNSPECIFIED
NSF Graduate Research FellowshipDGE-1745301
Caltech-Cambridge Exchange ProgramUNSPECIFIED
Subject Keywords:Addition reactions, Chemical structure, Ring opening reactions, Reactivity, Chemical calculations
Issue or Number:38
Record Number:CaltechAUTHORS:20200911-133135845
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Official Citation:Validation of the CoGEF Method as a Predictive Tool for Polymer Mechanochemistry. Isabel M. Klein, Corey C. Husic, Dávid P. Kovács, Nicolas J. Choquette, and Maxwell J. Robb. Journal of the American Chemical Society 2020 142 (38), 16364-16381; DOI: 10.1021/jacs.0c06868
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:105340
Deposited By: George Porter
Deposited On:14 Sep 2020 14:37
Last Modified:30 Sep 2020 19:37

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