S NMR spectroscopy. 4. Substituent effects on the ³³S nuclear quadrupole coupling constants and electric field gradient in 3- and 4-substituted benzenesulphonates studied by DFT calculations in vacuo and in aqueous solution

³³S nuclear quadrupole coupling constants (χ) and the principal component of the electric field gradient (qzz) in 3- and 4-substituted benzenesulphonates are dependent on the electronic properties of substituents. Previously reported experimental results were interpreted with the support of theoretical calculations in vacuo and in aqueous solution. To obtain good reproducibility of the experimental data, the introduction of the solvent effect into the calculations was mandatory. The best results were obtained at the B3LYP/6-311++G(3d,p) level using the Integral Equation Formalism for the Polarisable Continuum Model (IEF-PCM) to reproduce the solvent effect. In vacuo, for neutral substituents, the substituent effect on sulphur qzz can be mainly ascribed to electronic interactions (i.e., inductive and mesomeric effects transmitted through the aromatic ring). For charged substituents ( [Formula: see text] ) there is also a relevant contribution of coulomb origin, owed to the electric charge on the substituent itself, which polarises the S–O and C–S bonds. In aqueous solution, short-range solute–solvent interactions (i.e., hydrogen bonding) can be neglected, and the solvent effect can be adequately described considering the electrostatic interactions between the C–SO₃ ⁻ moiety and the electric charges on the surface of the cavity embedding the molecule within the solvent. These interactions amplify the electronic contribution transmitted through the aromatic ring and partially annihilate the coulomb contribution of the intrinsic charges of substituents. The results of the Natural Bond Orbital (NBO) analysis support these results and demonstrate that the polarisation of the S–O and S–C bonds and oxygen lone pairs due to solvent interactions produces only a redistribution of the electron density around the sulphur nucleus, thus inducing the variations of qzz.