High-field ESR on Light-Induced Transition of Spin Multiplicity in FeCo Complex

Abstract

Cyanide-bridged Fe-Co complex [Fe(Tp)(CN)₃]₂Co(bpe)⋅5H₂O (1⋅5H₂O; Tp = hydro-tris(pyrazolyl)borate; bpe = 1,2-bis(4-pyridyl)ethane) shows temperature- and light- induced metal-to-metal charge transfer (MMCT) involving spin state changes between magnetic $\mathrm{Fe}^{\mathrm{III}}_{\phantom{\mathrm{III}}\mathrm{LS}}\mbox{--}\mathrm{Co}^{\mathrm{II}}_{\phantom{\mathrm{II}}\mathrm{HS}}$ (HS = high spin, LS = low spin) state and nonmagnetic $\mathrm{Fe}^{\mathrm{II}}_{\phantom{\mathrm{II}}\mathrm{LS}}\mbox{--}\mathrm{Co}^{\mathrm{III}}_{\phantom{\mathrm{III}}\mathrm{LS}}$ state, while the dehydrated material 1 does not show any MMCT and holds $\mathrm{Fe}^{\mathrm{III}}_{\phantom{\mathrm{III}}\mathrm{LS}}\mbox{--}\mathrm{Co}^{\mathrm{II}}_{\phantom{\mathrm{II}}\mathrm{HS}}$ state. We have investigated the magnetic properties of each spin state in 1 and 1⋅5H₂O by means of magnetization and ESR measurement under pulsed high magnetic field. At low temperature below T _N, in both 1 and 1⋅5H₂O, the saturation magnetization in the induced ferromagnetic phase is well explained by S and g values derived from the magnetic susceptibility study. In the ESR of 1, we observed characteristic modes corresponding to a spin excitation in the induced ferromagnetic phase where its temperature dependence shows an evolution of spin correlation in the $\mathrm{Fe}^{\mathrm{III}}_{\phantom{\mathrm{III}}\mathrm{LS}}\mbox{--}\mathrm{Co}^{\mathrm{II}}_{\phantom{\mathrm{II}}\mathrm{HS}}$ state at low temperature. We further found that the similar ESR modes grow in the light-induced state of 1⋅5H₂O. The results strongly suggest that the light-induced magnetization in 1⋅5H₂O is driven by a light-induced MMCT, which involves transition of spin multiplicity from the nonmagnetic $\mathrm{Fe}^{\mathrm{II}}_{\phantom{\mathrm{II}}\mathrm{LS}}\mbox{--}\mathrm{Co}^{\mathrm{III}}_{\phantom{\mathrm{III}}\mathrm{LS}}$ to the magnetic $\mathrm{Fe}^{\mathrm{III}}_{\phantom{\mathrm{III}}\mathrm{LS}}\mbox{--}\mathrm{Co}^{\mathrm{II}}_{\phantom{\mathrm{\mathrm{II}}}\mathrm{HS}}$ pair.