Unusual binary aggregates of perylene bisimide revealed by their electronic transitions in helium nanodroplets and DFT calculations

The S1 ← S0 electronic transition of perylene bisimide (PBI) and its binary aggregates were investigated using a combination of helium nanodroplet isolation spectroscopy and computational methods. First, well-resolved vibronic bands of the PBI monomer obtained under the superfluid helium nanodroplet environment were compared to simulated vibronic spectra with anharmonic corrections of the band positions. Second, about ten sets of weaker vibronic bands were observed, which show similar vibronic patterns as that of the PBI monomer and have their band origins red-shifted by about 8 to 218 cm −1 . Experimental Poisson curve analyses, performed at the origins of these new sets of bands and the PBI monomer, indicate that the carriers of these weaker red-shifted vibronic bands are binary adducts of PBI. Three types of PBI dimer structures where the electronic transition dipole moments of the two subunits are perpendicular to each other were proposed as possible carriers of these red-shifted vibronic patterns. Extensive vibronic simulations were carried out in a multi-step procedure with TD-DFT, vertical Hessian, and finally adiabatic Hessian approaches. Small red-shifted band origins and very similar vibronic patterns to that of the monomer were predicted for unusual, T-shaped, type I dimer structures and are in close agreement with the experimental data. The combined experimental and theoretical results indicate that the helium nanodroplet environment enables the formation of these unusual T-shaped dimers and stabilizes them. The superfluid helium nanodroplet environment produces some uncharacteristic perylene bisimide dimer geometries which feature discrete red-shifted vibronic bands, in contrast to the usual π-stacked dimers observed in solution.