Study on spin configuration in photoresponsive iron mixed-valence complexes by Mössbauer spectroscopy

Abstract

We have investigated magnetic properties in a series of photoresponsive dithiooxalato (dto)-bridged iron mixed-valence complexes, (SP-R)[FeIIFeIII(dto)3] (SP-R = R-substituted pyridospiropyran cation; R = Me, Et, and Pr; abbreviated as 1 Me, 1 Et, and 1 Pr, respectively). As for our previous reports, 1 Me and 1 Et show two-step succeeding ferromagnetic transitions at T C = 25 & 8 K and 22 & 5 K, respectively. However, 1 Et has no hysteresis in the magnetic susceptibility, while 1 Me undergoes the charge transfer phase transition with thermal hysteresis around 75 K. To elucidate the two-step transitions of them, we measured 57Fe Mossbauer spectra of 1 Et. The spectra of FeII (S = 2) and FeIII (S = 1/2) in the HTP were observed in the magnetically ordered state as well as the paramagnetic state, and revealed that only HTP exists in a temperature range up to 5 K. The result is consistent with that of 1 Pr, where one ferromagnetic phase transition occurs at T C = 10 K. 57Fe Mossbauer spectroscopy is useful to clarify the origin of the succeeding magnetic transition for these systems.