Spin transition in [Fe(PM-BiA)(2)(NCS)(2)] studied by the electron paramagnetic resonance of the Mn2+ ion

The spin transition of Fe2+ ions in the mononuclear compound cis-bis(thiocy anato)-bis(N-2'-pyridylmethylene)-4-(aminobiphenyl)-iron(II) is studied by electron paramagnetic resonance (EPR) of Mn2+. In cooling the compound down to the temperature range 174-168 K, the Fe2+ ions undergo a complete trans ition from the high spin (HS, S = 2) to the low spin (LS, S = 0) state, occ urring with a narrow, similar to 5 K and unusually sharp hysteresis loop. T he temperature dependence of the unit cell parameters is almost linear on b oth sides of the spin transition; the variation of the unit cell parameters at the spin transition is very anisotropic. The EPR spectra, typical of th e Mn2+ ion, only gradually change with temperature in the two spin states o f Fe2+ but undergo a striking transformation in the spin transition range. This shows that a considerable cooperativity exists between the metal ions. Computer simulations using a laboratory-developed simulation program indic ate significant changes in the zero-field splitting (zfs) parameters in the course of the spin transition. Lower-than-axial symmetry of the environmen t of Mn2+ persists in both spin states of Fe2+; however, a stronger axial d istortion arises in the HS state. The temperature variations of the zfs parameter D are related to transforma tions of the crystal structure using the Newman superposition model amended for contributions of thermal expansion of the crystal lattice and lattice vibrations. Computer fits show a reduction of the model parameter-power law exponent-in the LS state, t(2) = 4, in comparison with the HS state, t(2) = 8. Such a tendency is consistent with the decrease of the Fe-N bond lengt hs in the HS to LS transition.