Photostability versus photodegradation in the excited-state intramolecular proton transfer of nitro enamines: competing reaction paths and conical intersections.
The phototautomerization mechanism of a model nitro enamine (NEA) chromophore (incorporated in the structure of a highly photolabile pesticide, tetrahydro-2-(nitromethylene)-2H-1,3-thiazine) has been studied using complete active space self-consistent field reaction path computations. The optically accessible 1pipi* excited state of NEA involves separation of charge and correlates diabatically with the ground state of the tautomerized acinitro imine (ANI) form. For optimum photostabilization, the 1pipi* state of NEA should be S1: in this case, the tautomer would be efficiently formed via a diabatic intramolecular proton-transfer pathway passing through an S1/S0 conical intersection, followed by a facile thermal back proton-transfer reaction. However, in NEA itself the lowest excited states correspond to nitro group 1npi* states, and there are additional surface crossings that provide a mechanism for populating the 1npi* manifold. The above results indicate that the high photolability observed for the pesticide [Kleier, D.; Holden, I.; Casida, J. E.; Ruzo, L. O. J. Agric. Food Chem. 1985, 33, 998-1000] has to be ascribed to photochemistry originating on the 1npi* manifold of states, populated indirectly from the 1pipi* state.
Migani
Annapaola
A
Institut de Química Computacional, Departament de Química, Universitat de Girona, Campus de Montilivi, 17071 Girona, Spain. amigani@stark.udg.es
Bearpark
Michael J
MJ
Olivucci
Massimo
M
Robb
Michael A
MA