Competition between Halogen Bonding and π-Hole Interactions Involving Various Donors: The Role of Dispersion Effects.

In this study several σ- and π-hole complexes between IF and pnicogen ZO2 F (Z=P, As), chalcogen ChO3 (Ch=S, Se) and tetrel TrOF2 (Tr=Si, Ge) -bearing compounds were optimized at the RI-MP2/def2-TZVPD level of theory. All complexes were characterized as minima by frequency analysis calculations. In addition, a comparative CCSD(T) and DFT (with and without dispersion correction) study using the BP86, B3LYP and M06-2X method was done in order to analyze the role of dispersion effects in the σ-/π-hole binding. Finally the Bader's AIM analysis of several complexes was performed to further characterize the interactions discussed herein.