Synthesis, Isolation, and Spectroscopic Characterization of Holmium‐Based Mixed‐Metal Nitride Clusterfullerenes: Ho_xSc_3−xN@C₈₀ (x=1, 2)

Abstract

The synthesis, isolation and spectroscopic characterization of holmium-based mixed metal nitride clusterfullerenes Ho(x) Sc(3-x) N@C(80) (x=1, 2) are reported. Two isomers of Ho(x) Sc(3-x) N@C(80) (x=1, 2) were synthesized by the reactive gas atmosphere method and isolated by multistep recycling HPLC. The isomeric structures of Ho(x) Sc(3-x) N@C(80) (x=1, 2) were characterized by laser-desorption time-of-flight (LD-TOF) mass spectrometry and UV/Vis/NIR, FTIR and Raman spectroscopy. A comparative study of M(x) Sc(3-x) N@C(80) (M=Gd, Dy, Lu, Ho) demonstrates the dependence of their electronic and vibrational properties on the encaged metal. Despite the distinct perturbation induced by 4f(10) electrons, we report the first paramagnetic (13) C NMR study on Ho(x) Sc(3-x) N@C(80) (I; x=1, 2) and confirm I(h) -symmetric cage structure. A (45) Sc NMR study on HoSc(2) N@C(80) (I, II) revealed a temperature-dependent chemical shift in the temperature range of 268-308 K.

An Expanded Family of Dysprosium–Scandium Mixed‐Metal Nitride Clusterfullerenes: The Role of the Lanthanide Metal on the Carbon Cage Size Distribution

“…[28] DySc 2 N@C 80 (II) and Dy 2 ScN@C 80 (II) C 80 -based NCFs including both homogeneous NCFs and MMNCFsh ave been extensively studied in recent years. [38] Similar to the cases of the reported M x Sc 3Àx N@C 80 (II, M = Gd, [14] Lu, [22] Ho, [26] (x = 1, 2) MMNCFs, the overall FTIR spectralf eatures of DySc 2 N@C 80 (II) and Dy 2 ScN@C 80 (II) are quite similart ot hose of Sc 3 N@C 80 (II, D 5h ) and Dy 3 N@C 80 (II, D 5h ), thus the isomeric cage structures of DySc 2 N@C 80 (II) and Dy 2 ScN@C 80 (II) can be unambiguously determined as C 80 -D 5h (6). The relativelyh igher yield of C 80 -based MMNCFsf acilitates the successfuli solationo fD y x Sc 3Àx N@C 80 (II) in this work.…”

Cluster-size dependent internal dynamics and magnetic anisotropy of Ho ions in HoM2N@C80and Ho2MN@C80families (M = Sc, Lu, Y)

“…28 Computations of Dc values at 268 and 308 K and an assumption of the weak temperature variation of the geometry-related term in eqn (1) predict that the 45 Sc paramagnetic shi should decrease by 285 ppm (compared to the experimentally measured decrease of 222 ppm). Fig.…”

Metallofullerenes Encaging Mixed‐Metal Clusters: Synthesis and Structural Studies of GdxHo3−xN@C80 and GdxLu3−xN@C80

“…Therefore, several mixed-metal nitride endofullerenes have been synthesized and isolated, such as Ce x M 3Àx N@C 78-88 (x = 1, 2; M = Sc, Y), [2] HoM 2 N@C 80 and Ho 2 MN@C 80 families (M = Sc, Lu, Y), [3] ScYErN@C 80 , [4] Lu x Y 3Àx N@C 80 , [5] Sc 2 TiN@C 80 , [6] Sc x Gd 3Àx N@C 80 , [4] DySc 2 N@C 80 , [7] Ho x Sc 3Àx N@C 80 (x = 1, 2), [8] and so forth. [1] In particular, mixed-metal nitride endofullerenes with two or three types of metal in the encaged cluster provide a platform for the preparation of multifunctional molecules.…”