The Influence of Halide Substituents on the Structural and Magnetic Properties of Fe${}_6$Dy${}_3$ Rings

We report the synthesis and magnetic properties of three new nine-membered Fe(III)-Dy(III) cyclic coordination clusters (CCCs), with a core motif of [Fe${}_6$Dy${}_3$(μ-OMe)${}_9$(vanox)${}_6$(X-benz)${}_6$] where the benzoate ligands are substituted in the para-position with X = F (1), Cl (2), Br (3). Single crystal X-ray diffraction structure analyses show that for the smaller fluorine or chlorine substituents the resulting structures exhibit an isostructural Fe${}_6$Dy${}_3$ core, whilst the 4-bromobenzoate ligand leads to structural distortions which affect the dynamic magnetic behavior. The magnetic susceptibility and magnetization of 1-3 were investigated and show similar behavior in the dc (direct current) magnetic data. Additional ac (alternating current) magnetic measurements show that all compounds exhibit frequency-dependent and temperature-dependent signals in the in-phase and out-of-phase component of the susceptibility and can therefore be described as field-induced SMMs. The fluoro-substituted benzoate cluster 1 shows a magnetic behavior closely similar to that of the corresponding unsubstituted Fe${}_6$Dy${}_3$ cluster, with U${}_{eff}$ = 21.3 K within the Orbach process. ... mehrBy increasing the size of the substituent toward 4-chlorobenzoate within 2, an increase of the energy barrier to U${}_{eff}$ = 36.1 K was observed. While the energy barrier becomes higher from 1 to 2, highlighting that the introduction of different substituents on the benzoate ligand in the para-position has an impact on the magnetic properties, cluster 3 shows a significantly different SMM behavior where U${}_{eff}$ is reduced in the Orbach regime to only 4.9 K.