³³S nuclear quadrupole resonance study of dibenzyl disulfide toward understanding of cross-linked structures in...

Experimental and theoretical investigations of a sulfur-33 electric-field-gradient (EFG) tensor of disulfide bonds in ³³S-labled dibenzyl disulfide have been presented. Temperature dependence of quadrupolar frequencies, ν_Q, is observed in the temperature range between 80 and 280 K, in which single peaks appear in all the ³³S nuclear quadrupole resonance (NQR) spectra. Analysis of nutation echo ³³S NQR spectra at 200 K yields the quadrupolar coupling constant, C_Q value, of 46.8(6) MHz and the asymmetry parameter, η_Q, of 0.48(7). The orientation of the ³³S EFG tensor of the disulfide is obtained by quantum chemical calculations: the largest EFG tensor component, V_ZZ, is approximately perpendicular to the molecular plane (C-S-S), and the smallest component, V_XX, is approximately 41° off the C-S bond. Extensive quantum chemical calculations are systematically performed to investigate dependences of ³³S EFG tensors on changes of torsion angles in disulfide and trisulfide bonds, indicating that analysis of ν_Q and C_Q values potentially makes it possible to assign the secondary structures of cross-linking in a rubber.