Herein we probe the effects that differing substituents and the identity of the halogen atom has on the electropositive σ-holes in halogen-containing halogen bond (XB) donors. The XB donors were fully optimized and characterized with the global hybrid M06-2X density functional in conjunction with a double-ζ quality correlation consistent basis set augmented with diffuse functions on all atoms and a pseudopotential on bromine, iodine, and astatine centers (aug-cc-pVDZ for H, C, N, O, F, Cl and aug-cc-pVDZ-PP for Br, I, At; denoted as aVDZ-PP). To gain insight into the role that changing the identity of the halogen atom and substituents (i.e., electron withdrawing and electron donating groups) perform on the size and magnitude of the σ-hole, natural bond orbital (NBO) and critical point analyses were employed on the M06-2X/aVDZ-PP optimized structures. Connections between the σ-hole properties and the structural, energetic, and vibrational properties of the XB donors will be discussed.

The positive side to halogens: A σ-hole study

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