title: Picosecond kinetics of excited-state charge separation in 4-(dimethylamino)pyridine.
abstract: 4-(Dimethylamino)pyridine (DMAP) shows solvent-dependent dual fluorescence from the initially excited state B* and a highly polar TICT state A*. Room-temperature time-resolved picosecond fluorescence investigations prove the bimodal kinetics of the excited-state electron transfer reaction B*-->A* in polar aprotic media. In medium polarity solvents (such as ethyl acetate) two emitting states of DMAP are shown to reach equilibrium within 50 ps. Both emitting states originate from the same ground state. The rate of excited-state charge separation depends on polarity and proton donating ability of the surrounding medium. The effects of temperature on the quantum yields of both fluorescences of DMAP in polar aprotic media indicate the transition from the kinetic regime (at low temperatures) to the equilibrium regime (at high temperatures). The kinetic behaviour of the dual luminescence of DMAP in protic solvents is more complex than in aprotic ones. In alcohols an efficient nonradiative channel competes with excited-state charge separation.
authors.affiliation: Institute of Physical Chemistry, Polish Academy of Sciences, Warsaw, Poland.
authors.forename: Izabela
authors.initials: I
authors.lastname: Szydłowska
authors.forename: Jacek
authors.initials: J
authors.lastname: Kubicki
authors.forename: Jerzy
authors.initials: J
authors.lastname: Herbich
mesh_terms: D015761:4-Aminopyridine / Q000031:analogs & derivatives* / Q000737:chemistry* / Q000528:radiation effects; D004735:Energy Transfer; D007700:Kinetics; D015394:Molecular Structure; D010777:Photochemistry; D012997:Solvents / Q000737:chemistry; D013050:Spectrometry, Fluorescence; D013696:Temperature; D013997:Time Factors; D014466:Ultraviolet Rays
chemical_list: D012997:Solvents; D015761:4-Aminopyridine; C003885:4-dimethylaminopyridine