title: Quenching of tryptophan (1)(pi,pi*) fluorescence induced by intramolecular hydrogen abstraction via an aborted decarboxylation mechanism.
abstract: CASSCF computations show that the hydrogen-transfer-induced fluorescence quenching of the (1)(pi,pi*) excited state of zwitterionic tryptophan occurs in three steps: (1) formation of an intramolecular excited-state complex, (2) hydrogen transfer from the amino acid side chain to the indole chromophore, and (3) radiationless decay through a conical intersection, where the reaction path bifurcates to a photodecarboxylation and a phototautomerization route. We present a general model for fluorescence quenching by hydrogen donors, where the radiationless decay occurs at a conical intersection (real state crossing). At the intersection, the reaction responsible for the quenching is aborted, because the reaction path bifurcates and can proceed forward to the products or backward to the reactants. The position of the intersection along the quenching coordinate depends on the nature of the states and, in turn, affects the formation of photoproducts during the quenching. For a (1)(n,pi*) model system reported earlier (Sinicropi, A.; Pogni, R.; Basosi, R.; Robb, M. A.; Gramlich, G.; Nau, W. M.; Olivucci, M. Angew. Chem., Int. Ed. 2001, 40, 4185-4189), the ground and the excited state of the chromophore are hydrogen acceptors, and the excited-state hydrogen transfer is nonadiabatic and leads directly to the intersection point. There, the hydrogen transfer is aborted, and the reaction can return to the reactant pair or proceed further to the hydrogen-transfer products. In the tryptophan case, the ground state is not a hydrogen acceptor, and the excited-state hydrogen transfer is an adiabatic, sequential proton and electron transfer. The decay to the ground state occurs along a second reaction coordinate associated with decarboxylation of the amino acid side chain and the corresponding aborted conical intersection. The results show that, for (1)(pi,pi*) states, the hydrogen transfer alone is not sufficient to induce the quenching, and explain why fluorescence quenching induced by hydrogen donors is less general for (1)(pi,pi*) than for (1)(n,pi*) states.
authors.affiliation: Department of Chemistry, King's College London, Strand, London WC2R 2LS, UK.
authors.forename: Lluís
authors.initials: L
authors.lastname: Blancafort
authors.forename: David
authors.initials: D
authors.lastname: González
authors.forename: Massimo
authors.initials: M
authors.lastname: Olivucci
authors.forename: Michael A
authors.initials: MA
authors.lastname: Robb
mesh_terms: D005453:Fluorescence; D006859:Hydrogen / Q000737:chemistry*; D015394:Molecular Structure; D014364:Tryptophan / Q000737:chemistry*
chemical_list: D006859:Hydrogen; D014364:Tryptophan