Iron(II) Spin Crossover Complexes Based on a Redox Active Equatorial Schiff-Base-Like Ligand.

Abstract

In this work, two iron(II) coordination compounds with a N2O2 coordinating Schiff base-like ligand bearing a redox active tetrathiafulvalene (TTF) unit and pyridine or trans-1,2-bis(4-pyridylethylene) as an axial ligand are synthesized. Crystals suitable for single X-ray structure analysis were obtained for the new ligand. The complexes were characterized by magnetic susceptibility measurements, T-dependent UV-vis spectroscopy, and cyclic voltammetry. Both complexes display spin transition behavior below room temperature with T1/2 values of 146 and 156 K. The mononuclear iron(II) complex [FeTTFL(py)2] is relatively stable up to 400 K compared to similar complexes, showing no loss of axial ligands upon heating. Temperature dependent Mössbauer spectroscopy was conducted for the coordination polymer {[FeTTFL(bpee)]}n to get more information regarding the origin of the stepwise spin crossover (SCO) behavior observed in the magnetic measurements. The change of the spin state is accompanied by a change of the optical properties, which can be monitored by VT-UV-vis spectroscopy for the mononuclear complex and has been analyzed in theoretical studies. The redox behavior of the iron(II) complexes reveals three reversible redox steps which are located at the iron center and at the TTF unit of the ligand. Oxidation of the TTF unit induces characteristic changes in the UV-vis spectrum that can be followed by spectroelectrochemical UV-vis spectroscopy. Addressing the potential of the iron-centered redox process results in similar changes in the UV-vis spectrum, which indicates an electronic coupling of the redox active unit with the metal center under certain circumstances.