Here we investigate the energetic, structural, and vibrational properties in a series of substituted chalcogen bond (ChB) donors. Full geometry optimizations and harmonic vibrational frequency computations are performed on each ChB donor with the global hybrid M06-2X density functional in conjunction with a triple-ζ quality correlation consistent basis set augmented with diffuse functions on all atoms and a pseudopotential on selenium and tellurium centers (aug-cc-pVTZ for H, C, N, O, F and aug-cc-pVTZ-PP for Se, Te; denoted aVTZ-PP). The nature of the electropositive σ-holes of the ChB donors are probed with electrostatic potential (ESP) and electron localization function (ELF) critical point analyses. To gain insight into the relationship between the strength of the σ-hole and various degrees of conjugation in the ChB donor, the magnitude of the conjugation is quantitatively evaluated using full NBO analyses on the M06-2X/aVTZ optimized geometries. Connections between select geometrical parameters, σ-hole strength, and angular dependence of the ChB donors will be discussed.

σ-Hole flexibility in chalcogen bond donors

ACS Spring 2022

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