High-Resolution Electronic Spectroscopy of the BODIPY Chromophore in Supersonic Beam and Superfluid Helium Droplets

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 BF(2) 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.