Effect of N-substitution in multinuclear complexes allows interplay between magnetic states and multistability investigated by Mössbauer spectroscopy

A series of pentadentate ligands N-X-5LH2 (X=H, Methyl, Benzyl)=N-X-saldptn (4-X-N,N′-bis(l-hydroxy-2-benzylidene)-1,7-diamino-4-azaheptane) has been prepared by a Schiff base condensation between 1,7-diamino-4-X-azaheptane and salicylaldehyde. Complexation with Fe(III) yields a series of high-spin (S=5/2) complexes of [FeIII(N-X-5L)Cl]. Such precursors were combined with [Mo(CN)8]4− and a series of blue nonanuclear cluster compounds [MoIV(CN)FeIII(N-X-5L)8]Cl4 resulted. Such star-shaped nonanuclear compounds are high-spin systems at room temperature. On cooling to 10K some of the iron(III) centers switched to the low-spin state as proven by Mossbauer spectra, i.e. multiple electronic trans…