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The Ground- and Excited-State (1nπ* and 1ππ*) Carboxylic Acid-Catalyzed Proton(Hydrogen Atom)-Transfer Energy Surfaces in 3-Formyl-7-azaindole

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Theoretical approaches on the ground- and excited-state proton (or hydrogen atom) transfer in the 3-formyl-7-azaindole (3FAI)/formic acid dual hydrogen-bonded complex were performed. In the ground state, theanalysis of the transition-state geometry led us to conclude a concerted, asynchronous proton-transfer patternthat correlates with the hydrogen-bonding strength. The lowest singlet excited state in the 3FAI/formic acidcomplex was calculated to be in an nπ* configuration. On the basis of frontier molecular orbital analyses, then → π* transition was concluded to originate from the carbonyl lone-pair electrons of the formyl substitute.A highly endergonic proton-transfer reaction barrier of ∼16.7 kcal/mol was calculated in the 1nπ* state at theCIS/6-31G(d‘,p‘) level of theory. The second excited singlet state possesses a ππ* configuration in which theexcited-state double proton transfer (ESDPT) takes place with a negligible energy barrier. The results providea theoretical rationalization of the competitive internal conversion/ESDPT mechanism previously proposedfor the 3FAI hydrogen-bonded complexes (J. Phys. Chem. A2000, 104, 8863).

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