Non-aqueous solutions of lithium and sodium perchlorates have been investigated by IR and Raman spectroscopy. The 35C104 and 37C10, isotopomers induce an asymmetry or a splitting of v3 and v, bands. All spectra are interpreted by assuming that the bands of possible solvent-separated species are at the same wavenumbers as if they were free ions ('spectroscopically free ions'). In ionizing solvents (dimethylsulfoxide, N,N-dimethylformamide, acetonitrile or acetone) these perchlorates are partly or completely dissociated into free ions while in associating solvents (esters, cyclic ethers or nitromethane) LiClO, is in part dimerized. In nitromethane, LiClO, ion pairs are slightly dissociated into free ions at low concentrations and dimerized at high concentrations. The coordination of ClO, in the ion pairs is either monodentate (LiClO,) or bidentate (NaClO,). Both ClO, groups in the LiClO, dimer are linked by two lithium bridges into a centrosymmetrical structure.
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