Static and MAS 35CI NMR and Molecular Motions of ClO −4 Ions in the Various Phases of Multimethylammonium Perchlorates

1986

Static and MAS*) 35CI NMR data of CIO−4 ions in the low-, intermediate- and high-temperature phases of trimethylammonium, dimethylammonium and monomethylammonium perchlorates are reported. The observed solid-solid phase transitions are interrelated with the motional state of the perchlorate ions. In the low-temperature phase III of trimethylammonium perchlorate there is an anisotropic motion of the ClO−4 ions with a constant quadrupole frequency of 185 kHz and an increasing value of the asymmetry parameter when approaching phase transition III-II. The activation energy for this motion is found to be 44.3 kj/mol. At the transition III-II the ClO−4 ions gain orientational degrees of freedom m…