G. Grabner et al., 2-STATE MODEL FOR THE PHOTOPHYSICS OF 9,9'-BIANTHRYL - FLUORESCENCE, TRANSIENT-ABSORPTION, AND SEMIEMPIRICAL STUDIES, The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 102(4), 1998, pp. 689-696
The photophysics of 9,9'-bianthryl (BA) were investigated by means of
fluorescence spectroscopy, nanosecond transient-absorption spectroscop
y, and semiempirical calculations. Fluorescence spectra and lifetimes
were measured in more than 50 solvents in order to get a detailed pict
ure of the solvent dependence. The results show that the fluorescence
lifetime is constant in solvents of low polarity (D < 5) and increases
with solvent polarity in more polar solvents. Departures from this tr
end can be traced to specific solute-solvent interactions. Excited-sta
te singlet-singlet absorption spectra were measured in the ultraviolet
range and show a marked solvent dependence. In polar solvents, the sp
ectrum (lambda(max) = 315 nm) is closely related to those of the radic
al ions of both BA and anthracene. The decay rate constant of this ban
d is identical with that of the fluorescence emission in a range of so
lvents of varying polarity (D > 5), thus providing direct proof of the
charge-separated character of the fluorescent state in polar solvents
. The 315 nm band is absent in isooctane, indicating that the fluoresc
ent state is not of charge-separated character in this case. Semiempir
ical calculations were carried out in order to rationalize the experim
ental data. Careful consideration of the symmetry character of the ele
ctronic states involved and of the solvent effect on these states indi
cates that two distinct transitions are responsible for the observed f
luorescence emission; in nonpolar solvents, a nonpolar state with D-2
symmetry and a torsion angle that is markedly smaller than 90 degrees
is the fluorescent state, whereas in polar solvents fluorescence origi
nates from a charge-separated perpendicular state of D-2d symmetry. Th
is latter state is responsible for the large solvent effects on fluore
scence and singlet-singlet absorption. Triplet-triplet absorption and
intersystem-crossing efficiency data were also measured in several sol
vents. They too are solvent-dependent but do not show characteristics
of charge separation; they rather are influenced by specific solute-so
lvent interactions.