Circular dichroism of diglycosyl dichalcogenides in solution and solid state

Solution and solid-state CD spectra of nine peracetylated and deacetalyted diglycosyl disulfides were measured to study the relationship between the low-energy CD transitions (n(1)->+sigma(S-S)* and n(2)->sigma(S-S)*) and helicity of the inherently chiral disulfide chromophore as perturbed by chiral carbohydrate moieties. The solid-state CD spectra were directly correlated with the reported X-ray structures of Ac(4)GlcSSGlcAc(4) and Ac(4)GlcSSGalAc(4), and the CD data revealed that all the disulfides have M helicity with Cl-S-S-Cl' dihedral angles -90 degrees < phi < 0 degrees both in solution and in the solid state. A TDDFT CD study was carried out on dimethyl diselenide which confirmed that the same quadrant rule is relevant between the signs of the low-energy CD transitions and the diselenide torsional angle as formulated previously for the disulfide chromophore. The CD spectra of Ac(4)GlcSeSeGlcAc(4) measured in solution and in the solid state were correlated with its X-ray structure and reproduced well by TDDFT CD calculations performed on its tetra-O-acetyl derivative.