Filling the gap between the quantum and classical worlds of nanoscale magnetism: giant molecular aggregates based on paramagnetic 3d metal ions

Abstract

In this review, aspects of the syntheses, structures and magnetic properties of giant 3d and 3d/4f paramagnetic metal clusters in moderate oxidation states are discussed. The term "giant clusters" is used herein to denote metal clusters with nuclearity of 30 or greater. Many synthetic strategies towards such species have been developed and are discussed in this paper. Attempts are made to categorize some of the most successful methods to giant clusters, but it will be pointed out that the characteristics of the crystal structures of such compounds including nuclearity, shape, architecture, etc. are unpredictable depending on the specific structural features of the included organic ligands, reaction conditions and other factors. The majority of the described compounds in this review are of special interest not only for their fascinating nanosized structures but also because they sometimes display interesting magnetic phenomena, such as ferromagnetic exchange interactions, large ground state spin values, single-molecule magnetism behaviour or impressively large magnetocaloric effects. In addition, they often possess the properties of both the quantum and the classical world, and thus their systematic study offers the potential for the discovery of new physical phenomena, as well as a better understanding of the existing ones. The research field of giant clusters is under continuous evolution and their intriguing structural characteristics and magnetism properties that attract the interest of synthetic Inorganic Chemists promise a brilliant future for this class of compounds.

Antimony-ligated dysprosium single-molecule magnets as catalysts for stibine dehydrocoupling

“…8 The pioneering work on SMMs focused on exchange-coupled transition metal cage compounds, 9,10 and monometallic 3d complexes have recently emerged as another important class of SMM. 11–13 Many of the most exciting developments in single-molecule magnetism have been accounted for by the lanthanides terbium, dysprosium and erbium, 14–19 and lanthanide SMMs have been described with very high U eff values and magnetic blocking temperatures.…”

Magnetism and Photomagnetism of Prussian Blue Analogue Nanoparticles Embedded in Porous Metal Oxide Ordered Nanostructures

“…The first one, which can be termed "molecular magnets", focuses on the study of magnetic states, the control of their lifetimes and coupling of magnetism with other properties. Thus, the rational design of molecular entities with foreseeable exchange interactions and/or magnetocrystalline anisotropy resulted in the development of room-temperature magnets, [1][2][3][4] singlemolecule magnets [5][6][7][8][9] or single-chain magnets. [10][11][12][13] Prussian blue analogues (PBAs) are characteristic of this field.…”

Topological insights in polynuclear Ni/Na coordination clusters derived from a schiff base ligand

“…These entities are of great interest for their aesthetically beautiful structures [2][3][4], unexpected transformations [5][6][7] and potential applications in magnetism [8][9][10], luminescence [11][12][13][14][15], catalysis [16][17][18], etc. Paramagnetic transition metal CCs are of intense interest and have attracted a vast amount of attention since the discovery that some CCs behave as single-molecule magnets (SMMs) [19][20][21].…”