Slow magnetic relaxation in a homo dinuclear Dy(iii) complex in a pentagonal bipyramidal geometry

Abstract

We hereby report a dinuclear Dy(III) complex, [Dy(LH3)Cl2]2·2Et2O (1) (LH4 = 2,3-dihydroxybenzylidene)-2-(hydroxyimino)propanehydrazide) where both the metal centres are in a pentagonal bipyramidal (PBP) geometry with the axial positions being occupied...

Zero‐field Slow Magnetic Relaxation Behavior of Dy2 in a Series of Dinuclear {Ln2} (Ln=Dy, Tb, Gd and Er) Complexes: A Combined Experimental and Theoretical Study

“…For both the Dy centers, the computed orientation of the main magnetic axis of the ground state KD is perpendicular to the disk type shape spin‐density and passes closely (∼20° degree) through one of the shortest ‐O atoms of the ‐hthd ligand (see Figure 6). CASSCF computed beta spin‐density of the ground state reveals a typical disk‐like flattened shape, a characteristic electron density representation of oblate shaped m J |±15/2⟩ state of Dy(III) ions [9,36,90–95] . A close inspection of the spin‐density and orientation of the main magnetic axis reveals that each eight coordinated Dy III ions possess four axial (−O atoms of hthd ligands) and four equatorial bonds (coordinating atoms in the molecular plane).…”

“…Thus, designing and isolating dinuclear SMMs in a controlled manner, one can build larger motifs using a bottom‐up approach and construct SMMs with higher effective energy and blocking temperature. So, the synthesis of dinuclear complexes with small modifications in their coordination environments can be a promising approach to gain desired knowledge on complicated magnetic interactions and the effect of anisotropy on its magnetic dynamics [35–45] . For example, the modification of the terminal group on the ligand has been known to enhance the energy barrier dramatically by stabilizing the ground Kramers doublet (KDs) [46–48] .…”

Structural and magnetic studies of six-coordinated Schiff base Dy(iii) complexes

“…Their Dy–Cl and Dy–O distances and Cl–Dy–Cl, Cl–Dy–O and O–Dy–O angles (Tables S2 and S4† for 1 and 2 , respectively) are comparable to the corresponding reported values, respectively. 33–39 Each Dy( iii ) ion in 2 behaves as a 3-connected node and is further linked to another three Dy( iii ) ions through three simple linkers of H 2 L 2 , forming a two-dimensional sheet (Fig. S19b†) of 2 .…”

“…The distorted octahedral DyO 4 Cl 2 geometry (Table S11 † S2 and S4 † for 1 and 2, respectively) are comparable to the corresponding reported values, respectively. [33][34][35][36][37][38][39] Each Dy(III) ion in 2 behaves as a 3-connected node and is further linked to another three Dy(III) ions through three simple linkers of H 2 L 2 , forming a two-dimensional sheet (Fig. S19b † In this work, the tuning of the coordination environments of DyO x Cl 6−x in the title metal complexes was achieved by adjusting the spacer between the two nitrogen atoms in the bis-Schiff base ligands as depicted in Scheme 1, which eventually gave four metal complexes with three different kinds of coordination environments.…”

Synthesis, Structure, and Zero-Field SMM Behavior of Homometallic Dy2, Dy4, and Dy6 Complexes

“…There is considerable recent interest in the utility of appropriate lanthanide metal complexes as single-molecule magnets (SMMs) and single-ion magnets (SIMs). − This field got its breakthrough by the seminal discovery of Ishikawa and co-workers that the terbium phthalocyanine sandwich complex [Bu 4 N]­[TbPc 2 ] is a single-molecule magnet with slow relaxation of magnetization . This discovery prompted researchers to examine the favorable properties of lanthanide ions including a large unquenched spin–orbit coupling, which can result in substantial single-ion anisotropy .…”