QUENCHING PROCESSES IN HYDROGEN-BONDED PAIRS - INTERACTIONS OF EXCITED FLUORENONE WITH ALCOHOLS AND PHENOLS

In order to clarify mechanisms of excited state interactions in hydrog en-bonded pairs, we have studied the kinetics of dynamic quenching of singlet and triplet fluorenone by a series of alcohols, phenols, and r elated compounds, in which hydrogen-bonding power, redox potential, an d acidity are systematically varied. In addition, effects of solvent b asicity or polarity and deuteration help identify the role of hydrogen -bonding in physical or chemical quenching processes. Alcohols and wea k acids, with high oxidation potentials, do not quench the triplet, bu t quench the singlet at rates which parallel hydrogen-bonding power. T his is attributed to a physical mechanism, involving vibronic coupling to the ground state via the hydrogen bond. This is much stronger in t he excited state than in the ground state, and provides efficient ener gy dissipation in the radiationless transition. Phenols, with hydrogen -bonding power comparable to that of the alcohols but with much lower oxidation potentials, quench both singlet and triplet by electron or H -atom transfer, depending on potentials, acidities, and solvent polari ty, as shown by formation of anion or neutral fluorenone radicals from the triplet. Rates increase with both decreasing oxidation potential of the phenol and increasing acidity of the incipient cation radical. Quenching proceeds via a hydrogen-bonded complex and is facilitated by proton transfer contributions to the effective excited state redox po tential.