Mixed dysprosium-lanthanide nitride clusterfullerenes DyM₂N@C₈₀-I_hand Dy₂MN@C₈₀-I_h(M = Gd, Er, Tm, and Lu): synthesis, molecular structure, and quantum motion of the endohedral nitrogen atom

Abstract

The impact of the second metal on the synthesis and molecular structure of Dy–M nitride clusterfullerenes (M = Gd, Er, Tm, Lu) is evaluated systematically.

Endohedral Metallofullerenes: New Structures and Unseen Phenomena

“…Noteworthily, an interesting report from Olmstead and co‐workers detailed a systematic study analyzing the pyramidalization of the M 3 N (M=Gd, Tb, Dy, Ho, Er, Tm, Lu, and Sc) units inside the I h (7)‐C 80 cage, revealing that the M 3 N unit becomes pyramidalized to some extent when the sum of the Shannon–Prewitt crystal radii of the three metal ions involved exceeds 3.05 Å, and this result is applicable to endohedrals in which all three metal ions are identical or totally different . Consistently, Popov and colleagues confirmed that in the mixed‐metal NCFs, DyM 2 N@ I h (7)‐C 80 (M=Er, Gd), the N atom in DyEr 2 N is located in the plane of DyEr 2 (Figure c), whereas the DyGd 2 N cluster is pyramidal with the sum of the three M‐N‐M angles of 345.9° (Figure d), as the Gd atom is too large to maintain the planarity of the cluster in C 80 .…”

“… Molecular structures of (a) Ho 3 N@ C 2 (22010)‐C 78 , (b) Tb 3 N@ C 2 (22010)‐C 78 , (c) DyEr 2 N@ I h (7)‐C 80 , and (d) DyGd 2 N@ I h (7)‐C 80 . Fused pentagon pairs are highlighted in red.…”

Gadolinium as an accelerator for reaching thermal equilibrium and its influence on the ground state of Dy2GdN@C80 single-molecule magnets

“…Dy 2 GdN@C 80 endofullerenes were produced by arcdischarge synthesis using the corresponding metals [15]. The subsequent separation by high-pressure liquid chromatography resulted in a sample of 95% purity with 5% Dy 3 N@C 80 contamination as inferred from time-of-flight mass spectrometry [25].…”

“…First magnetic studies were performed on Gd@C 82 [12], and it took 17 more years until SMM behavior in endohedral fullerenes was found with DySc 2 N@C 80 [13]. In the following many different C 80 mixed dysprosium-lanthanide nitride clusters have been synthesized and magnetically characterized [14][15][16]. As in other radical bridged lanthanide complexes [17] dysprosium ion pairs appear to form excellent SMMs [18].…”

Single‐Molecule Magnets DyM2N@C80 and Dy2MN@C80 (M=Sc, Lu): The Impact of Diamagnetic Metals on Dy3+ Magnetic Anisotropy, Dy⋅⋅⋅Dy Coupling, and Mixing of Molecular and Lattice Vibrations

“…For this, we chose lutetium as a diamagnetic lanthanide, the ionic radius ( R 3+ =0.86 Å) of which is noticeably larger than that of scandium ( R 3+ =0.75 Å). Yet, as we reported recently, DyLu 2 N@C 80 ‐ I h and Dy 2 LuN@C 80 ‐ I h can still be synthesized, albeit in lower yields than the dysprosium‐scandium analogues . The larger size of Lu 3+ leads to changes in the internal structure of the trimetallic nitride cluster, and in particular results in shorter Dy−N bonds than in the dysprosium‐scandium NCFs.…”