Covalency versus magnetic axiality in Nd molecular magnets: Nd-photoluminescence, strong ligand-field, and unprecedented nephelauxetic effect in fullerenes NdM₂N@C₈₀ (M = Sc, Lu, Y)

Abstract

Nd-based nitride clusterfullerenes NdM2N@C80 with rare-earth metals of different sizes (M = Sc, Y, Lu) were synthesized to elucidate the influence of the cluster composition, shape and internal strain on...

Capturing Metal Fluoride inside a Carbon Cage

“…These short Gd–F bonds are in part due to the strong bonding interaction between the hard acidic Gd 3+ cation and the hard basic F – anion, which is the most electronegative element in the periodic table. In addition, the confinement of fullerene cage further contributes to the shortened metal-nonmetal bonds as demonstrated in other EMFs. , …”

“…In addition, the confinement of fullerene cage further contributes to the shortened metal-nonmetal bonds as demonstrated in other EMFs. 34,35 S2. As shown in Figure 2b, the two Gd atoms both reside under a hexagonal carbon ring on the cage, featuring a η 6 coordination mode.…”

Fullerene rotation dictated by benzene–fullerene interactions

“…1–4 Elucidating the structures of these metallofullerenes with single-crystal X-ray diffraction proved powerful in understanding these novel molecules. 5–14 Determining the structure with high accuracy is fundamentally important to understand their properties such as bonding interactions between the entities of metallofullerenes and the crystal field around the metal ions. 15–23 The ubiquitous disorders (more than 95%) in metallofullerene crystals originate from the round shape of fullerene cages, which tend to rotate in the crystal lattice, and the shallow potential energy surface supplied by the fullerene cage to hold the encapsulated metal ions.…”

“…24–26,29,30 Trimetallic nitride clusterfullerenes have attracted broad interest since their discovery. 6,31 A diversified combination of the metal ions from transition and rare-earth metals produces molecules with fascinating single-molecule magnetism represented by DyM 2 N@C 80 and Dy 2 MN@C 80 (M = Sc, 32–36 Y, 37,38 La, 38 ErSc, 39 Lu, 40 or V 41 ). 42 The combination of cluster rotation with mixed metals presents a great challenge in their structural elucidation by single crystal X-ray diffraction because the overlapping between different metal ions precludes their accurate assignment.…”