Is There a Single Ideal Parameter for Halogen-Bonding-Based Lewis Acidity?

Halogen-bond donors (halogen-based Lewis acids) have now found various applications in diverse fields of chemistry. The goal of this study was to identify a parameter obtainable from a single DFT calculation that reliably describes halogen-bonding strength (Lewis acidity). First, several DFT methods were benchmarked against the CCSD(T) CBS binding data of complexes of 17 carbon-based halogen-bond donors with chloride and ammonia as representative Lewis bases, which revealed M05-2X with a partially augmented def2-TZVP(D) basis set as the best model chemistry. The best single parameter to predict halogen-bonding strengths was the static σ-hole depth, but it still provided inaccurate predictions for a series of compounds. Thus, a more reliable parameter, Ωσ* , has been developed through the linear combination of the σ-hole depth and the σ*(C-I) energy, which was further validated against neutral, cationic, halogen- and nitrogen-based halogen-bond donors with very good performance.