Solvent dependence of the spectra and kinetics of excited-state charge transfer in three (alkylamino)benzonitriles

Steady-state absorption and emission spectra and emission decay kinetics are reported for 4-aminobenzonitrile (ABN), 4-(1-azetidinyl)benzonitrile (P4C), 4-(1-pyrrolidiny1)benzonitrile (P5C), and 4-(1-piperidiny1)benzonitrile (P6C) in 24 room temperature solvents. In solvents of modest to high polarity, P4C, P5C, and P6C exhibit dual fluorescence and emission decays characteristic of the transformation from an initially prepared (LE) state to a more polar charge transfer (CT) state, whereas ABN does not undergo this reaction. The frequencies of the steady-state absorption and emission spectra of all of these solutes can be rationalized using a dielectric continuum description of the solvent and considering only the minima on the reactive surfaces, which are assumed to involve both an intramolecular (twisting) and a solvation coordinate. Characteristics of the gas-phase solutes deduced from this analysis are in good agreement with electronic structure calculations and indicate that differences in their spectra mainly reflect differences in the relative energies of the gas-phase LE and CT states. The relative yields of LE and CT emission are not described as satisfactorily by this model, and reasons for this failure are discussed. The kinetics of the LE → CT reaction vary considerably with solute and solvent. In many solvents, the emission decays of P4C are reasonably described by a simple two-state kinetic scheme with time-independent rate constants. In PSC and P6C multiexponential decays are observed that reflect time-dependent shifts of the component spectra as well as time-dependent reaction rates. A simplified analysis of these complex dynamics provides estimates for both the free energy change Δ _rG and (average) LE → CT rate constant fe for a wide range of solute and solvent combinations. The driving force for reaction ( - Δ _rG) follows the order P6C > P5C > P4C and increases with increasing solvent polarity. The reaction rates are correlated to Δ _rG and follow the opposite trend. The relationships observed between k _f and Δ _rG suggest that static solvent effects, i.e., barrier height changes, are the primary determinants of the solvent dependence in P4C. Correlations between barrier-corrected rates and solvation times suggest that dynamical solvent effects contribute substantially to the solvent dependence of the rates in PSC, and especially P6C.