Modulating the Roaming Dynamics for the NO Release in ortho-Nitrobenzenes

The dynamics of NO release upon photodissociation of nitroaromatic compounds is dependent on the nature of the interaction between the NO2 group and substituent in the ortho position. A bimodal (slow and fast) translational energy distribution of the NO photofragment indicates the presence of two di...

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Bibliographic Details
Published in:The journal of physical chemistry letters 2023-03, Vol.14 (11), p.2816-2822
Main Authors: Bejoy, Namitha Brijit, Roy Chowdhury, Prahlad, Patwari, G. Naresh
Format: Article
Language:English
Subjects:
Physical Insights into Chemistry, Catalysis, and Interfaces
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Summary:The dynamics of NO release upon photodissociation of nitroaromatic compounds is dependent on the nature of the interaction between the NO2 group and substituent in the ortho position. A bimodal (slow and fast) translational energy distribution of the NO photofragment indicates the presence of two distinct NO elimination channels. The slow-to-fast branching ratio for the NO release is regulated by the hydrogen bonding ability of the ortho substituent and follows the order [OH > NH2 > CH3 > OCH3], indicating that the intramolecular hydrogen bonding plays a pivotal role in NO release dynamics. Further, the topology of the triplet state potential energy surface acts as a doorway to the dissociation pathway switching between the roaming and nonroaming mechanisms, with hydrogen bonding substituents (OH and NH2) favoring the roaming mechanism.
ISSN:1948-7185
1948-7185
DOI:10.1021/acs.jpclett.3c00134