Utilization of diamagnetic Zn(II) ion to boost the anisotropic nature of Ln(III) ion in heterodinuclear Zn(II)–Ln(III) single‐molecule magnets

Abstract

A series of dimetallic Zn II -Ln III compounds of general formulae [LnZn (L) 3 (NO 3 ) 2 ]Á2CH 3 OH (Ln III = Dy III (1), Tb III (2), Gd III (3)) was prepared by stepwise reaction of compartmental ligand LH = ((E)-2-((pyridin-2-ylmethylene)amino)phenol) with Ln (NO 3 ) 3 ÁxH 2 O and Zn (NO 3 ) 2 ÁxH 2 O in the presence of triethylamine as base. The single crystal XRD analysis indicated that both metallic ions are connected to each other through phenolic oxygen atom from fully deprotonated ligand. Based on the SHAPE analysis, the Dy III ion has nine coordination numbers with distorted spherical capped square antiprism geometry, while the Zn II ion has six coordination numbers with distorted octahedral geometry. DC magnetic studies reveal the existence of antiferromagnetic inter-

Syntheses, Structures, and Magnetic Properties of Novel [3×1 + 2×1] Pentanuclear Zinc(II)-Lanthanide(III) Cocrystal Complexes: Slow Magnetic Relaxation Behavior of the Dy(III) Analogue

“…At 300 K, the experimental χ M T values are 8.06 cm 3 ·K·mol –1 for 1 , 11.96 cm 3 ·K·mol –1 for 2 , and 14.32 cm 3 ·K·mol –1 for 3 respectively, which are close to the expected value of one uncoupled Ln III ion (7.88 cm 3 ·K·mol –1 , 8 S 7/2 , S = 7/2, g = 2 for 1 , 11.81 cm 3 ·K·mol –1 , 7 F 6 , S = 3, L = 3, g = 3/2 for 2 and 14.17 cm 3 ·K·mol –1 , 6 H 15/2 , S = 5/2, L = 5, g = 4/3 for 3 ). In the case of 1 , as the temperature drops, the χ M T values found to be almost constant down to 15 K and then decrease dramatically to reach the lowest χ M T value of 7.61 cm 3 ·K·mol –1 at 2 K. The sudden downtrend can be put down to the presence of weak antiferromagnetic coupling between Gd III ions and/or zero-field splitting (ZFS) effects of the Gd III ions. − …”

Tetranuclear CoII4O4 Cubane Complex: Effective Catalyst Toward Electrochemical Water Oxidation

“…95 Some major difficulty in synthetic chemistry is creating a ligand that is suitable to bind with multiple metal ions through their coordination sites to create a polynuclear entity. 96 To meet this challenge, researchers have employed polydentate Schiff base ligands. 97,98 These ligands possess multiple coordination sites and flexible coordination arms, which allow them to coordinate with different metal ions.…”

“…Consequently, these features lead to an increase in the energy barrier ( U eff ) for the magnetization relaxation in SMMs . Some major difficulty in synthetic chemistry is creating a ligand that is suitable to bind with multiple metal ions through their coordination sites to create a polynuclear entity . To meet this challenge, researchers have employed polydentate Schiff base ligands. , These ligands possess multiple coordination sites and flexible coordination arms, which allow them to coordinate with different metal ions. , Additionally, their oxygen donors can form short bridges between metal ions, providing a suitable structure for diverse topologies in polynuclear clusters. , …”

Effect of diamagnetic Zn(ii) ions on the SMM properties of a series of trinuclear ZnDy2 and tetranuclear Zn2Dy2 (LnIII = Dy, Tb, Gd) complexes: combined experimental and theoretical studies

“…[42][43][44][49][50][51] Recent studies proposed that an increase in the number of Zn II ions corresponds to a decrease in U eff ; 45,46,52 however, this is in conflict with the hypothesis that an increase in the number of Zn II ions should enhance the energy barrier as they provide a "dilution effect" of the complex. [47][48][49][50][51][52][53][54][55] So, it has become necessary to understand the interaction between the number of Zn II ions and its relation to the energy barrier. To our understanding, the strategic manipulation of the electronic density distribution within specific directions of Dy III coordination geometries-specifically, enhancing or reducing axial/equatorial charge distributions around Dy III -is a pivotal challenge for advancing the SMM properties of Zn−Dy complexes.…”