The magnet-like behavior can beobserved by slow relaxation of the magnetization below theblocking temperature. Since the discovery of SMMs in theearly 1990s, this assumption has formed the basis for theunderstanding of the origin of the anisotropic barrier.However, in recent years the development of novel lantha-nide-only SMMs that challenge and defy this theory pose anumber of questions:

A Polynuclear Lanthanide Single-Molecule Magnet with a Record

The unique advantages and the exciting application prospects of AIEgens have triggered booming developments in this area in recent years. Among them, stimuli-responsive AIEgens have received particular attention and impressive progress, and they have been demonstrated to show tremendous potential in many fields from physical chemistry to materials science and to biology and medicine. Here, the recent achievements of stimuli-responsive AIEgens in terms of seven most representative types of stimuli including force, light, polarity, temperature, electricity, ion, and pH, are summarized. Based on typical examples, it is illustrated how each type of systems realize the desired stimuli-responsive performance for various applications. The key work principles behind them are ultimately deciphered and figured out to offer new insights and guidelines for the design and engineering of the next-generation stimuli-responsive luminescent materials for more broad applications.

Stimuli-Responsive AIEgens

Molecular magnetism, though distinctly a field within chemistry, encompasses much more than synthesis and has strong links with other disciplines across the physical sciences. Research goals in this area are currently dominated by magnetic memory and quantum information processing but extend in other directions toward medical diagnostics and catalysis. This review focuses on two popular subtopics, single-molecule magnetism and molecular spin qubits, outlining their design and study and some of the latest outstanding results in the field. The above topics are complemented by an overview of pertinent electronic structure methods and, in a look towards the future, an overview of the state of the art in measurement and modeling of molecular spin–phonon coupling. Expected final online publication date for the Annual Review of Materials Research, Volume 52 is July 2022. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

Molecular Magnetism

Recent studies have shown that mononuclear lanthanide (Ln) complexes can be high-performing single-molecule magnets (SMMs). Recently, there has been an influx of mononuclear Ln alkoxide and aryloxide SMMs, which have provided the necessary geometrical control to improve SMM properties and to allow the intricate relaxation dynamics of Ln SMMs to be studied in detail. Here non-aqueous Ln alkoxide and aryloxide chemistry applied to the synthesis of low-coordinate mononuclear Ln SMMs are reviewed. The focus is on mononuclear DyIII alkoxide and aryloxide SMMs with coordination numbers up to eight, covering synthesis, solid-state structures and magnetic attributes. Brief overviews are also provided of mononuclear TbIII , HoIII , ErIII and YbIII alkoxide and aryloxide SMMs.

https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/chem.202100085

Mononuclear Dysprosium Alkoxide and Aryloxide Single-Molecule Magnets.

Emerging Trends on Designing High-Performance Dysprosium(III) Single-Molecule Magnets

Four 3d-4f heterometallic complexes based on salicylhydroxamic acid (H3sha) have been synthesized. Single-crystal X-ray diffraction analysis reveal that all complexes are comprised of {Dy[12-MCsha,Mn(III)-4]}n (n = 2 or 3, MC = metallacrown) supramolecular architectures, where the MC building blocks are further ligated by the ditopic subunit ligands with different lengths and bite angles. Along with the angular orientations ranging from 120° to 180°, the resulting architectures vary from dimeric double-layer to trimeric triangular MC assemblies based on the building block and directional bonding approaches. Magnetic measurements reveal the presence of dominant antiferromagnetic interactions for all complexes, thereinto, one of which displays slow relaxation of magnetization under external dc field.

Building Block and Directional Bonding Approaches for the Synthesis of {DyMn4}n (n = 2, 3) Metallacrown Assemblies

Single-ion magnet and luminescent properties in a Dy(III) triangular dodecahedral complex

We report a trinuclear dysprosium single-molecule magnet, [Dy3(μ3-CO3)(Clbbpen)3](CF3SO3)·6MeCN, which has a perfectly equilateral triangular structure. The Ising-like anisotropy of each Dy(III) site is oriented almost normal to the triangular plane, and magnetic dipole interactions between the spins cause an antiparallel Ising ground state. Crossing of the antiferromagnetic states by the ferromagnetic state occurs at ca. 0.2 T and gives rise to a characteristic step in magnetic hysteresis loops. This molecule thus serves as a perfectly triangular model system to explore frustrated Ising anisotropy.

/pdf/a-perfect-triangular-dysprosium-single-molecule-magnet-with-19ychrg429.pdf

A perfect triangular dysprosium single-molecule magnet with virtually antiparallel Ising-like anisotropy

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Building Block and Directional Bonding Approaches for the Synthesis of {DyMn4}n (n = 2, 3) Metallacrown Assemblies

Single-ion magnet and luminescent properties in a Dy(III) triangular dodecahedral complex

A perfect triangular dysprosium single-molecule magnet with virtually antiparallel Ising-like anisotropy