title: Photophysical and spectroscopic manifestations of the low-lying pisigma* state of 4-(dimethylamino)benzethyne: solvent-polarity dependence of fluorescence and excited-state absorptions.
abstract: A concerted experimental and computational study of 4-(dimethylamino)benzethyne, DMABE, has been carried out to probe the low-lying pisigma* state and the role it plays in the photophysics of the molecule. The subpicosecond transient absorption spectra reveal the presence of a strong excited-state absorption at about 700 nm and a weaker absorption at about 520 nm. The observed absorption maxima are in excellent agreement with the TDDFT calculations that place a strongly allowed pisigma* <--pisigma* transition at 750 nm, and a weaker pipi* <--pipi* (LE) transition at 528 nm. This agreement combined with the differing decay times, and differing solvent shifts of the two transients, allow assignments of the 700 nm absorption to the pisigma* state and the 520 nm absorption to the LE (pipi*) state. The bifurcation of the initially excited L(a) (pipi*) state into the pisigma* state and the LE state, as probed by transient absorption, is strongly influenced by solvent polarity, with polar environments favoring the L(a)-->pisigma* decay channel over the competing L(a)--> LE decay channel. The nanosecond radiationless decay of the LE state to the dark pisigma* state is also strongly enhanced in polar environments, thus accounting for the dramatic quenching of fluorescence in solvents of high polarity.
authors.affiliation: Department of Chemistry and The Center for Laser and Optical Spectroscopy, The University of Akron, Akron, OH 44325-3601, USA.
authors.forename: Takashige
authors.initials: T
authors.lastname: Fujiwara
authors.forename: Jae-Kwang
authors.initials: JK
authors.lastname: Lee
authors.forename: Marek Z
authors.initials: MZ
authors.lastname: Zgierski
authors.forename: Edward C
authors.initials: EC
authors.lastname: Lim