Direct Microscopic Analysis of Individual C 60 Dimerization Events: Kinetics and Mechanisms

• Published in: Journal of the American Chemical Society Vol. 139; no. 50; pp. 18281 - 18287
• Main Authors: Okada, Satoshi, Kowashi, Satori, Schweighauser, Luca, Yamanouchi, Kaoru, Harano, Koji, Nakamura, Eiichi
• Format: Journal Article
• Language: English
• Published: United States 20-12-2017
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.7b09776

Modern transition state theory states that the statistical behavior of a chemical reaction is the sum of individual chemical events that occur randomly. Statistical analysis of each event for individual molecules in a three-dimensional space however is practically impossible. We report here that kinetics and mechanisms of chemical reactions can be investigated by using a one-dimensional system where reaction events can be observed in situ and counted one by one using variable-temperature (VT) atomic-resolution transmission electron microscopy (TEM). We thereby provide direct proof that the ensemble behavior of random events conforms to the Rice-Ramsperger-Kassel-Marcus theory, as illustrated for [2 + 2] cycloaddition of C
molecules in carbon nanotubes (CNTs). This method gives kinetic and structural information for different types of reactions occurring simultaneously in the microscopic view field, suggesting that the VT-TEM opens a new dimension of chemical kinetics research on molecules and their assemblies in their excited and ionized states. The study carried out at 393-493 K showed that pristine CNT primarily acts as a singlet sensitizer of the cycloaddition reaction that takes place with an activation energy of 33.5 ± 6.8 kJ/mol. On the other hand, CNT suffers electron damage of the conjugated system at 103-203 K and promotes a reactive radical cation path that takes place with an activation energy of only 1.9 ± 0.7 kJ/mol. The pre-exponential factor of the Arrhenius plot gave us further mechanistic insights.