Raman study of tetraglyme-LiClO4 solvate structures

Lithium perchlorate has been dissolved in tetra(ethylene glycol) dimethyl ether (tetraglyme or G4) to obtain (G4)(n)-LiClO4 mixtures with 1/2 less than or equal to n less than or equal to 80. The conformational changes and ionic interactions occurring in the crystalline and liquid phases as a function of temperature and salt concentration have been investigated by Raman spectroscopy. This spectroscopic characterization is based on previous vibrational assignments of free'' and coordinated perchlorate anions and on structural results obtained for the (G4)(1):LiAsF6 and (G4)(1/2):LiBF4 crystalline complexes. In crystalline (G4)(1):LiClO4, the ligands adopt, as in (G4)(1):LiAsF6, a double-helix dimer structure in which two six-coordinated Li+ cations are coordinated by two G4 molecules forming solvent separated ion pairs (SSIP) with the two anions. The two corresponding anions, however, are spectroscopically distinct as shown by their nu(1) vibrations at similar to931 and 928 cm(-1). In the (G4)(n)-LiClO4 liquid phase for n greater than or equal to 1, an equilibrium occurs between SSIP and monodentate contact ion pairs (CIP-I) characterized by nu(1) components at 932 and 939 cm(-1), respectively. For n < 1, a new nu(1) component appears at 945 cm(-1) in both the crystalline and liquid phases. It suggests the formation of aggregate interactions consisting of linear [Li+center dot center dot center dot(ClO4-)(2)](n) ionic chains.