Role of the Diamagnetic Zinc(II) Ion in Determining the Electronic Structure of Lanthanide Single‐Ion Magnets

Abstract

Abstract Four complexes containing Dy III and Pr III ions and their Ln III –Zn II analogs have been synthesized in order to study the influence that a diamagnetic Zn II ion has on the electronic structure and hence, the magnetic properties of the Dy III and Pr III single ions. Single‐crystal X‐ray diffraction revealed the molecular structures as [Dy III (HL) 2 (NO 3 ) 3 ] ( 1 ), [Pr III (HL) 2 (NO 3 ) 3 ] ( 2 ), [Zn II Dy III (L) 2 (CH 3 CO 2 )(NO 3 ) 2 ] ( 3 ) and [Zn II 2 Pr III (L) 2 (CH 3 CO 2 ) 4 (NO 3 )] ( 4 ) (where HL=2‐methoxy‐6‐[( E )‐phenyliminomethyl]phenol). The dc and ac magnetic data were collected for all four complexes. Compounds 1 and 3 display frequency dependent out‐of‐phase susceptibility signals ( χ M “ ), which is a characteristic signature for a single‐molecule magnet (SMM). Although 1 and 3 are chemically similar, a fivefold increase in the anisotropic barrier ( U eff ) is observed experimentally for 3 (83 cm −1 ), compared to 1 (16 cm −1 ). To rationalize the larger anisotropic barrier ( 1 vs. 3 ), detailed ab initio calculations were performed. Although the ground state Kramer's doublet in both 1 and 3 are axial in nature ( g zz =19.443 for 1 and 18.82 for 3 ), a significant difference in the energy gap ( U eff ) between the ground and first excited Kramer's doublet is calculated. This energy gap is governed by the electrostatic repulsion between the Dy III ion and the additional charge density found for the phenoxo bridging ligand in 3 . This extra charge density was found to be a consequence of the presence of the diamagnetic Zn II ion present in the complex. To explore the influence of diamagnetic ions on the magnetic properties further, previously reported and structurally related Zn–Dy III complexes were analyzed. These structurally analogous complexes unambiguously suggest that the electrostatic repulsion is found to be maximal when the Zn‐O‐Dy‐O dihedral angle is small, which is an ideal condition to maximize the anisotropic barrier in Dy III complexes.