Breaking a dative bond with mechanical forces

• Published in: Nature communications Vol. 12; no. 1; p. 5635
• Main Authors: Chen, Pengcheng, Fan, Dingxin, Zhang, Yunlong, Selloni, Annabella, Carter, Emily A., Arnold, Craig B., Dankworth, David C., Rucker, Steven P., Chelikowsky, James R., Yao, Nan
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 24.09.2021; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 14/3; 14/63; 147/138; 639/301/357; 639/638/263/910; 639/638/298/303; Atomic force microscopes; Atomic force microscopy; Carbon monoxide; Chemical bonding; Chemical bonds; Chemical reactions; CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; Computer applications; Covalent bonds; Humanities and Social Sciences; MATERIALS SCIENCE; Mechanical properties; Microscopes; Microscopy; multidisciplinary; Nanoscale materials; Reaction mechanisms; Science; Science & Technology - Other Topics; Science (multidisciplinary); Shear forces
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-021-25932-6

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. Controlled breaking of a chemical bond by mechanical forces can provide key insight into reaction mechanisms. Here the authors, using atomic force microscopy and computations, measure the forces involved in breaking a single dative bond between a CO molecule and a ferrous phthalocyanine complex.