Breaking a dative bond with mechanical forces

Pengcheng Chen; Dingxin Fan; Yunlong Zhang; Annabella Selloni; Emily A Carter; Craig B Arnold; David C Dankworth; Steven P Rucker; James R Chelikowsky; Nan Yao

doi:10.1038/s41467-021-25932-6

Breaking a dative bond with mechanical forces

Nat Commun. 2021 Sep 24;12(1):5635. doi: 10.1038/s41467-021-25932-6.

Authors

Pengcheng Chen^#¹, Dingxin Fan^#², Yunlong Zhang³, Annabella Selloni⁴, Emily A Carter^{5

6}, Craig B Arnold^{1

5}, David C Dankworth⁷, Steven P Rucker⁷, James R Chelikowsky^{8

9

10}, Nan Yao¹¹

Affiliations

¹ Princeton Institute for the Science and Technology of Materials, Princeton University, Princeton, NJ, 08540-8211, USA.
² McKetta Department of Chemical Engineering, University of Texas at Austin, Austin, TX, 78712-1589, USA.
³ ExxonMobil Research and Engineering Company, Annandale, NJ, 08801-3096, USA. [email protected].
⁴ Department of Chemistry, Princeton University, Princeton, NJ, 08544-0001, USA.
⁵ Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ, 08544-5263, USA.
⁶ Office of the Chancellor and Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, Los Angeles, CA, 90095-1405, USA.
⁷ ExxonMobil Research and Engineering Company, Annandale, NJ, 08801-3096, USA.
⁸ McKetta Department of Chemical Engineering, University of Texas at Austin, Austin, TX, 78712-1589, USA. [email protected].
⁹ Department of Physics, University of Texas at Austin, Austin, TX, 78712-1192, USA. [email protected].
¹⁰ Center for Computational Materials, Oden Institute for Computational Engineering and Sciences, University of Texas at Austin, Austin, TX, 78712-1229, USA. [email protected].
¹¹ Princeton Institute for the Science and Technology of Materials, Princeton University, Princeton, NJ, 08540-8211, USA. [email protected].

^# Contributed equally.

Abstract

Bond breaking and forming are essential components of chemical reactions. Recently, the structure and formation of covalent bonds in single molecules have been studied by non-contact atomic force microscopy (AFM). Here, we report the details of a single dative bond breaking process using non-contact AFM. The dative bond between carbon monoxide and ferrous phthalocyanine was ruptured via mechanical forces applied by atomic force microscope tips; the process was quantitatively measured and characterized both experimentally and via quantum-based simulations. Our results show that the bond can be ruptured either by applying an attractive force of ~150 pN or by a repulsive force of ~220 pN with a significant contribution of shear forces, accompanied by changes of the spin state of the system. Our combined experimental and computational studies provide a deeper understanding of the chemical bond breaking process.