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We present the fluorescence excitation and dispersed emission spectra of the parent compound of the boron dipyrromethene (BODIPY) dye class measured in a supersonic beam and isolated in superfluid helium nanodroplets. The gas‐phase spectrum of the isolated molecules displays many low‐frequency transitions that are assigned to a symmetry‐breaking mode with a strongly nonharmonic potential, presumably the out‐of‐plane wagging mode of the BF2 group. The data are in good agreement with transition energies and Franck–Condon factors calculated for a double minimum potential in the upper electronic state. The corresponding transitions do not appear in the helium droplet. This is explained with the quasi‐rigid first layer of helium atoms attached to the dopant molecule by van der Waals forces. The spectral characteristics are those of a cyanine dye rather than that of an aromatic chromophore.
Electronic spectroscopy of molecules profits greatly from superfluid helium droplets serving as a gentle cryogenic matrix. Characteristic features of electronic spectra in helium droplets are a solvent shift, phonon wings, and in rare cases a splitting of zero phonon lines. For the majority of molecules investigated so far in helium droplets the vibrational fine structure in electronic spectra resembles what was observed in a supersonic jet. The electronic spectra of three methylated anthracene derivatives and one phenylated anthracene discussed in this paper reveal remarkable effects in the vibrational fine structure due to solvation in helium droplets.
For all four compounds the vibrational frequencies were almost not affected by the helium environment. However, if the electronic excitation is accompanied by nuclear rearrangement, the spectra showed remarkable line broadening in helium droplets. This is the case for 2-methylanthracene and 9-phenylanthracene. The corresponding line shape was of Lorentzian type and, thus, attributed to damping of the excited system by the helium environment. According to the linewidth the damping time constant was determined to be about 0.3 ps in the case of 2-methylanthracene and 0.1 ps for 9-phenylanthracene.