FT-Raman spectra of some polyiodides and of a series of <i>D</i>·I<sub>2</sub> chargetransfer complexes (where <i>D</i> is a molecule containing the thione or selone groups as donors), all characterized by x-ray diffraction, are reported. For the adducts with the thione compounds, which can be considered weak or medium-weak complexes, an empirical linear correlation between the frequency of the <i>v</i>(I-I) stretching vibrations and the <i>d</i>(I-I) bond distances has been found. Some polyiodides show FT-Raman spectra that are indistinguishable with respect to those displayed by the neutral complexes of weak or medium-weak strength; in such cases, the polyiodide can be regarded as a diiodine molecule, perturbed by an I<sub><i>n</i></sub><sup>-</sup> (<i>n</i> = 1, 3, ...) donor. Polyiodides of this type show Raman absorptions falling in the linear correlation.
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