Electrical and Spectral Properties of Complexes of Pyridine N-Oxide Derivatives with Iron Trichloride

Abstract

Complexes (1 : 2) of iron trichloride with N-oxides of pyridine, picolines, and 2,6-lutidine were studied by optical spectroscopy, dielectrometry, and conductometry. In solid complexes, three crystalline phases are in equilibrium; the nuclei of each of these phases can be detected in the oily state. The enthalpies of the coordination bonds are different in different phases. One of the phases of the 3-picoline N-oxide complex shows a strong orientation disorder; disappearance of the short-range order causes weakening of the coordination bonds by ∼1.6 kcal. The thermal motion of free base molecules in two phases of the 2,6-lutidine N-oxide complex is gaslike. In the solid phase of this complex, there is a strong distribution of the relaxation frequencies; the mean relaxation frequency is close to 220 Hz. Upon irradiation of the complexes with solar or UV light, specific coloration centers can form. Weak alternating electric fields initiate in some compounds reversible chemical reactions. The intermolecular and charge equilibria in the compounds are very labile; the energy of generation of the low-temperature electrical conductivity in them is close to 0.9 eV.