Intermolecular Hydrogen Abstraction from Hydroxy Group and Alkyl by T₁(ππ*) of 1-Chloro-4-nitronaphthalene

Nanosecond transient absorption and theoretical calculations have been used to investigate the intermolecular hydrogen abstractions from alcohols and 1-naphthol by the lowest excited triplet (T₁) of 1-chloro-4-nitronaphthalene upon excitation of the compound in organic solvents. The hydrogen abstraction of T₁ from hydroxy group of 1-naphthol takes place through an electron transfer followed by a proton transfer through hydrogen bonding interaction with rate constants of ∼10⁹ M^-1 s^-1. Hydrogen-bonding is crucial in this process, indicated by the observation of a half reduction for T₁ yield when increasing the concentration of 1-naphthol. The hydrogen abstraction in this way can be decelerated by increasing solvent polarity and hydrogen-bonding donor ability. The T₁ of 1-chloro-4-nitronaphthalene can undergo one-step H atom abstraction from alkyl hydrogen in alcoholic solvents, with rate constants of ∼10⁴ M^-1 s^-1, and produce radical intermediates with the absorption maximum at 368 nm. DFT calculation results indicate both oxygens of the nitro group are active sites for hydrogen abstraction, and the difference of activation barriers for formation of two radical isomers is only 1.0 kcal/mol.