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

Abstract

The synthesis of a large family of heterobimetallic lanthanide copper sulfates was realized via stoichiometric hydrothermal reactions among Ln2O3, CuO, and H2SO4, giving rise to four distinct phases, namely Ln2Cu­(SO4)2(OH)4 (Ln = Sm–Ho) (LnCuSO 4 -1), Ln4Cu­(SO4)2(OH)10 (Ln = Tm–Lu) (LnCuSO 4 -2), LnCu­(SO4)­(OH)3 (Ln = Nd–Gd, except Pm) (LnCuSO 4 -3), and LnCu­(SO4)­(OH)3 (Ln = Dy–Lu) (LnCuSO 4 -4), with completely different topologies. The passage from LnCuSO 4 -1 and LnCuSO 4 -3 to LnCuSO 4 -2 and LnCuSO 4 -4 across the 4f series, respectively, can be ascribed to the effect of lanthanide contraction, which progressively induces shrinking of the Ln–O distance, reduction in the Ln coordination number, and eventually structural transitions. The incorporation of identical 3d–4f metal ions into different spin–lattices, in conjunction with substitution of diverse Ln3+ cations within the same spin–lattice, gives rise to tunable magnetic properties varying from ferromagnetic ordering in GdCuSO 4 -3 and HoCuSO 4 -4 to antiferromagnetic ordering in YbCuSO 4 -4, and to paramagnetic correlations found in GdCuSO 4 -1 and YbCuSO 4 -2.

Rare‐Earth Single‐Atom Catalysts: A New Frontier in Photo/Electrocatalysis

“…[77,78] However, as a result of the quantum nature of d-f exchange interactions, the 3d-4f-5d orbitals are strongly coupled, and this has been exploited in several applications, such as Curie temperature ferromagnetic spintronics, optoelectronic materials, electro-pinned materials, high-density (HD) magnetic storage materials, and energy-level-gradient metallic materials. [79][80][81] In particular, because of the location of the 4f energy levels in RE oxides, the 4f electrons are strongly localized, but delocalization is increased by hybridization with light elements (such as oxygen via the 2p orbital), and this can result in covalent interactions. [82] For example, the band structure of lanthanide oxides reveals that the 4f orbitals form subbands in the valence region, allowing overlap with the oxygen p-band, demonstrating the ability to engineer the electronic structure of 4f elements by combination with lighter elements for bond activation.…”

Russian Doll-like 3d–4f Cluster Wheels with Slow Relaxation of Magnetization

“…However, the performances of these reported SMMs are still far from expected. Furthermore, there are a lot of other issues to be solved, such as the effective regulation and enhancement of magnetic coupling between 3d and 4f metal ions and the explanation of the relaxation mechanism [25][26][27][28]. Therefore, it is still of great significance to design and synthesize more 3d-4f SMMs with novel structures to improve SMM performances and to understand the magneto-structural correlation.…”

Two SiO44–-Templated Ln23Ni20 Clusters with Magnetic Cooling and Stability

“…Extensive research studies have concentrated on the development of high-nuclearity metal aggregation during the past few decades because of their fascinating topological frameworks and numerous properties. − As an important part of metal nanoclusters, high-nuclearity transition–lanthanide (3d-4f) metal clusters have gained increasing attentions from various fields, owing to a variety of charming structures and interesting chemical and physical properties resulting from the interactions of mixed-metal ions. − Especially, due to the distinct magnetic exchange interactions, 3d-4f clusters play an important role in the magnetocaloric effect (MCE) and are regarded as the environmentally friendly magnetic cooling materials, such as Gd 20 Ni 21 , Gd 102 Ni 36 , Gd 54 Ni 54 , Gd 42 Co 10 , Gd 45 Co 7 , and Gd 95 Co 60 . − Although a large class of researchers tried their best to construct 3d-4f nanoclusters with a large MCE, it is still a big challenge to assemble high-nuclearity 3d-4f heterometallic clusters, which is caused by the sundry coordination modes of 3d and 4f metal ions and the insolubility originating from the overaggregation of metal ions. − …”