Issue 33, 2014

Hydrogen bonding tunes the early stage of hydrogen-atom abstracting reaction

Abstract

The spontaneous and collision-assisted hydrogen-atom abstracting reaction (HA) dynamics of triplet benzil are investigated through the combination of transient absorption spectroscopy with TD-DFT calculations. HA dynamics exhibit a remarkable dependence on the hydrogen donor properties. The effects of the triplet-state hydrogen bonding on the reaction dynamics are illustrated. In particular, it is experimentally observed that strengthened triplet-state hydrogen bonding could accelerate the HA, whereas weakened triplet-state hydrogen bonding would postpone the HA. The triplet-state hydrogen bonding has great influences on the early stage of the HA reaction, while the bond dissociation energy of the hydrogen donors determines the subsequent reaction pathways. Protic solvents could sustain longer lifetimes of the excited-state intermediate formed after HA than non-protic solvents by 10 μs. This investigation provides insights into the HA dynamics and guidance to improve the product efficiency of photochemical reactions.

Graphical abstract: Hydrogen bonding tunes the early stage of hydrogen-atom abstracting reaction

Supplementary files

Article information

Article type
Paper
Submitted
29 Mar 2014
Accepted
10 Jun 2014
First published
16 Jun 2014

Phys. Chem. Chem. Phys., 2014,16, 17828-17834

Author version available

Hydrogen bonding tunes the early stage of hydrogen-atom abstracting reaction

Y. Yang, L. Liu, J. Chen and K. Han, Phys. Chem. Chem. Phys., 2014, 16, 17828 DOI: 10.1039/C4CP01371A

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