A study of the magnetic,molecular and electronic structure of some alkali biphenyl ion pairs in the solid state

A magnetic resonance and susceptibility study of the molecular and magnetic structure of some alkali biphenyl (Bp) polyglyme single crystals and powders has been performed. For RbBp · 2Ttg (Ttg=tetraglyme), space group C2/c, and NaBp · 2Tg (Tg=triglyme), space group P2₁, the average g tensors have been measured. From the average g tensor and the known crystal structure of RbBp · 2Ttg the molecular g tensor of the Bp anion could be derived. The molecular g tensor was calculated with Stone's theory. Excellent agreement was found with the experimental values. With the aid of the molecular g tensor of the Bp anion and the average g tensor of NaBp · 2Tg, for which the crystal structure is unknown, the orientation of the symmetry axes of Bp with respect to the crystal axes could be calculated. Susceptibility measurements reveal ferromagnetic coupling in both KBp · 2Ttg and NaBp · 2Tg, whereas antiferromagnetic coupling exists in RbBp · 2Ttg. The results of alkali N.M.R. experiments are related to the molecular structure. A lower limit is found for the electrical conductivity of NaBp · 2Tg.