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(1-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 Fe^III(N–X–⁵L)Cl]. Such precursors were combined with Mo(CN)₈]^4? and a series of blue nonanuclear cluster compounds Mo^IV{(CN)Fe^III(N–X–⁵L)}₈]Cl₄ resulted. Such star-shaped nonanuclear compounds are high-spin systems at room temperature. On cooling to 10 K some of the iron(III) centers switched to the low-spin state as proven by Mössbauer spectra, i.e. multiple electronic transitions. Parts of the compounds perform a high-spin to high-spin transition. Under light irradiation the populations are altered slightly.