Trends in σ-hole strengths and interactions of F3MX molecules (M = C, Si, Ge and X = F, Cl, Br, I)

It is well-established that many covalently-bonded atoms of Groups IV-VII have directionally-specific regions of positive electrostatic potential (sigma-holes) through which they can interact with negative sites. In the case of Group VII, this is called "halogen bonding." We have studied two series of molecules: the F3MX and, for comparison, the H3MX (M = C, Si and Ge; X = F, Cl, Br and I). Our objective was to determine how the interplay between M and X in each molecule affects the sigma-holes of both, and consequently their interactions with the nitrogen lone pair of HCN. We find that the relative electronegativities of M and X are not sufficient to explain their effects upon each other's sigma-holes; consideration of charge capacity/polarizability (and perhaps other factors) also appears to be necessary. However the results do support the description of normal sigma-hole interactions as being largely electrostatically-driven.