0000000000299888
AUTHOR
Milan Gembický
Spin crossover in a tetranuclear Cr(III)-Fe(III)3 complex
A novel heteronuclear exchange-coupled complex [Cr I I I {(CN)Fe I I I -( 5 L)} 3 (CN) 3 ] containing a pentadentate blocking ligand 5 L was synthesized. The X-ray structure shows that a meridional isomer applies with inequivalent Fe I I I centers. The complex exhibits a thermally induced spin crossover along with the exchange coupling. Mossbauer spectra indicate a spin transition between S = ½ and S = 5/2 states although a considerable amount of Fe I I I centers stays high-spin at T = 6 K. The magnetization, the magnetic susceptibility, and the Mossbauer data were fitted in one run with a spin crossover model taking into account exchange interactions among all metal centers.
Spin crossover in mononuclear and binuclear iron(III) complexes with pentadentate Schiff-base ligands
Abstract A series of mononuclear hexacoordinate iron(III) complexes, [Fe( 5 L )(py)]BPh 4 , and binuclear hexacoordinate iron(III) complexes, [( 5 L )Fe(μ 2 -bpy)Fe( 5 L )](BPh 4 ) 2 , has been prepared and their magnetic properties were investigated; the pentadentate ligands were derivatives of 5 L =saldptn=N,N′-bis(2-hydroxybenzyliden)-1,7-diamino-4-azaheptane. Temperature variation of the effective magnetic moment for them shows that a spin transition from the low-spin to the high-spin state occurs. The magnetic data were fitted to an Ising-like model appropriate for the mono- and binuclear systems.
A heptanuclear Fe(II)–Fe(III)6 system with twelve unpaired electrons
Abstract The pentadentate ligand 5 LH2 = saldptn = N,N′-bis(1-hydroxy-2-benzyliden)-1,7-diamino-4-azaheptane has been prepared by a Schiff base condensation between 1,7-diamino-4-azaheptane and the corresponding salicyaldehyde. Its complexation with Fe(III) gave the high-spin (S=5/2) complex of [Fe III ( 5 L)Cl]. This precursor was combined with [Fe(CN)6]4− and a blue heptanuclear complex [FeII{(CN)Fe III ( 5 L)}6]Cl2 resulted. This system belongs to the class of high-spin molecules possessing twelve unpaired electrons (S=6) as proven by the magnetic susceptibility measurements and Mossbauer spectra.