An endor and ESR study of the radical cation of N,N′-bis-(4-fluorophenyl)-4,4′-bipyridylium dichloride

The ESR and ENDOR spectra of the radical cation of N,N′-bis-(4-fluoro-phenyl)-4-4′-bipyridylium dichloride (fluorophenylquat FPQ) in methanol was studied over a temperature range from +_40° to ?90°. The ENDOR technique was used to obtain accurately the splitting constans for a highly complicated ESR spectrum and computer simulation showed excellent agreement. Fluorine ENDOR resonance was clearly observed with a line width similar to that of the protons. On decreasing the temperature the concentration of the radical cation decreases until at ?90° the ESR intensity was very small. This process is reversible and concentration studies indicate that the radical cation is in equilibrium with a diamagnetic dimer species. The thermodynamic parameters ΔH°, ΔG° and ΔS° for the process are reported.