Arraying Octahedral {Cr₂Dy₄} Units into 3D Single-Molecule-Magnet-Like Inorganic Compounds with Sulfate Bridges

Abstract

Two novel 3D pure inorganic compounds based on [CrDy(μ-O)(μ-OH)] cluster units and sulfate anions are presented. Both complexes exhibit single-molecule-magnet (SMM)-like behavior. Permutation of the magnetic moment direction among SMM-like cluster units has a significant effect on the performance of molecular nanomagnets, and directional consistency shows obvious advantages.

Asymmetric Assembly of Chiral Lanthanide(III) Tetranuclear Cluster Complexes Using Achiral Mixed Ligands: Single-molecule Magnet Behavior and Magnetic Entropy Change

“…Recently, lanthanide­(III) cluster complexes have attracted great attention in the field of single-molecule magnets (SMMs) and magnetic refrigeration molecular materials, , which is closely related to the large spin value of lanthanide­(III) ions. If the specified lanthanide­(III) ions such as dysprosium­(III) ions have strong magnetic anisotropy, they are suitable for the construction of SMMs, and when the specified lanthanide­(III) ions are gadolinium­(III) ions, they are suitable for the assembly of magnetic refrigeration molecule materials, owing to the largest ground state spin value ( S Gd = 7/2) and no magnetic anisotropy. , Because the magnetic axis and the symmetry of each dysprosium­(III) ion in the cluster complex are difficult to control, the research progress of dysprosium­(III) cluster complexes in the SMM field is relatively slow. However, gadolinium­(III) cluster complexes have obvious advantages in the study of magnetic refrigeration molecular materials. − …”

Single-Molecule Magnet Behavior of 1D Coordination Polymers Based on DyZn2(salen)2 Units and Pyridin-N-Oxide-4-Carboxylate: Structural Divergence and Magnetic Regulation

“…In recent years, we are very interested in the coordination polymers behaving as SMMs, because their nodes can be viewed as highly ordered SMMs in the dimension extension space, and the orientation and arrangement of such nodes may have an obvious effect on SMM properties; moreover, the guest molecules may be used to adjust SMM properties for microporous coordination polymers . We hope to link DyZn 2 (salen) 2 SMM units with organic bridging ligands for construction of coordination polymers maintaining SMM properties.…”

Structural Complexity and Magnetic Orderings in a Large Family of 3d–4f Heterobimetallic Sulfates

“…29,30 Despite the abundance of homometallic transition-metal-, lanthanide-, and actinide-bearing sulfate complexes, heterobimetallic materials templated by sulfates are relatively uncommon. Examples of these include YM(OH) 3 (SO 4 ) (M = Cu, Ni), 31 Ln 2 Cu(SO 4 ) 2 (OH) 4 (Ln = S m − D y ) , 3 2 , 3 3 C e 35 and a family of lanthanide transition-metal tellurite sulfates RE 2 M(TeO 3 ) 2 (SO 4 ) 2 reported in our previous works. 36,37 With the aim of expanding the structural diversity and investigating the magneto−structural correlations of 3d−4f heterobimetallic sulfates, herein we conducted hydrothermal reactions among the whole family of lanthanide (except Pm) oxides, copper oxide, and sulfuric acid.…”

“…As one of the most common inorganic oxoanion with a T d symmetry, sulfate can coordinate with metal ions in diverse ways, including terminal monodentate, terminal bidentate, bridging bidentate, and bridging tridentate, contributing to the structural intricacy of the resulting networks, polynuclear clusters, and even supramolecular assemblies. , Sulfate has proven to be an excellent chelating ligand in the construction of transition-metal hydroxysulfates. − In addition, the unexpected structural complexity of lanthanide sulfate complexes with topologies ranging from a one-dimensional (1D) chain to two-dimensional (2D) layered structures and three-dimensional (3D) frameworks is achieved by adopting a simple sulfate ligand. − Due to the high Lewis acidity of tetravalent actinide cations, the coordination chemistry is further complicated by their strong tendency to hydrolyze in solutions, resulting in the crystallization of polynuclear M IV oxohydroxo sulfate clusters, which can function as secondary building units for open frameworks. , Despite the abundance of homometallic transition-metal-, lanthanide-, and actinide-bearing sulfate complexes, heterobimetallic materials templated by sulfates are relatively uncommon. Examples of these include YM­(OH) 3 (SO 4 ) (M = Cu, Ni), Ln 2 Cu­(SO 4 ) 2 (OH) 4 (Ln = Sm–Dy), , Ce 13 Cr­(HSO 4 ) 6 (SO 4 ) 21 (H 2 O) 75 , [Ln 4 Cr 2 O 2 (OH) 4 (H 2 O) 9 (SO 4 ) 5 ]·3H 2 O (Ln = Gd–Dy), and a family of lanthanide transition-metal tellurite sulfates RE 2 M­(TeO 3 ) 2 (SO 4 ) 2 reported in our previous works. , …”