Proton-transfer tautomerism of beta-carbolines mediated by hydrogen-bondedcomplexes

The carboxylic acid catalyzed excited-state amino-imino tautomerism for bet a -carboline beta -CB) and its analogues has been investigated. Thermodynam ics and microsolvation (i.e., stoichiometry of the complex formation) of va rious beta -CB/acetic acid complexes in nonpolar solvents have been studied by means of absorption and emission titration experiments. Supplementary s upport of the stoichiometric ratio and structure for the hydrogen-bonding f ormation was provided by molecular design and syntheses of various P-CB ana logues incorporating either only one hydrogen bonding site or dual hydrogen bonding sites where interplay between two sites are sterically prohibited. The results in combination with time-resolved measurements and theoretical approaches suggest the 1:2 beta -CB/acetic acid complex with a structure o f triple hydrogen bonding formation to be responsible for the excited-state proton-transfer tautomerism in cyclohexane. The proton transfer time is be yond the response limit of the detecting system of 15 ps, indicating that o nly a negligibly small geometry adjustment is required for the guest molecu le (i.e., acetic acid) to a correct geometry, i.e., a hydrogen-bond relay c onfiguration, for the triple proton transfer to proceed. In comparison, for the 1: 1 beta -CB/acetic acid non-hydrogen-bond relayed complexes, amino-i mino tautomerism. is prohibited during the excited-state lifetime, giving r ise to a normal Stokes shifted emission. The results provide detailed groun d-state thermodynamics of beta -CB HB complexes as well as the dynamics of proton-transfer tautomerism. mediated by the hydrogen-bonding structures.