Blending Non‐Group‐3 Transition Metal and Rare‐Earth Metal into a C₈₀ Fullerene Cage with D_5h Symmetry

Abstract

Rare‐earth metals have been mostly entrapped into fullerene cages to form endohedral clusterfullerenes, whereas non‐Group‐3 transition metals that can form clusterfullerenes are limited to titanium (Ti) and vanadium (V), and both are exclusively entrapped within an Ih‐C80 cage. Non‐Group‐3 transition‐metal‐containing endohedral fullerenes based on a C80 cage with D5h symmetry, VxSc3−xN@D5h‐C80 (x=1, 2), have now been synthesized, which exhibit two variable cluster compositions. The molecular structure of VSc2N@D5h‐C80 was unambiguously determined by X‐ray crystallography. According to a comparative study with the reported Ti‐ and V‐containing clusterfullerenes based on a Ih‐C80 cage and the analogous D5h‐C80‐based metal nitride clusterfullerenes containing rare‐earth metals only, the decisive role of the non‐Group‐3 transition metal on the formation of the corresponding D5h‐C80‐based clusterfullerenes is unraveled.

How Does Spin Play with the Cycloaddition to Paramagnetic Endohedral Metallofullerenes? The Curious Case of TiSc2N@C80

“…Such a radical-like intermediate can be further stabilized by attaching typical π-withdrawing substituents to BD, which is shown to indeed boost up the addition reactions. The [4 + 3] stepwise addition mechanism discovered for TiSc 2 N@C 80 in this work might apply as well to other paramagnetic EMFs, 69−71 especially the structurally analogous TiY 2 N@I h -C 80 , 72−74 V x Sc 3−x N@I h -C 80 (x = 1, 2), 75 V x Sc 3−x N@D 5h -C 80 (x = 1, 2), 76 which have been recently synthesized in the lab with chemical properties yet to be established.…”

Capturing the Missing Carbon Cage Isomer of C84 via Mutual Stabilization of a Triangular Monometallic Cyanide Cluster

“…This tendency is consistent with their optical bandgaps, confirming the determinative role of the isomeric cage structure on the electronic property of an endohedral fullerene. 6,9,11 Spectroscopic and Electrochemical Study. UV−vis−NIR spectra of MCN@C 2 (13)-C 84 (M = Y, Dy, Tb) and DyCN@ C 2v (17)-C 84 dissolved in toluene were recorded on a UV−vis−NIR 3600 spectrometer (Shimadzu, Japan) using a quartz cell of 1 mm layer thickness and 1 nm resolution.…”

“…Moreover, to our knowledge the influence of the encapsulated metal on the metal−cage interactions of CYCF has never been studied, which is however important for understanding the unique structure and stability of CYCFs. C 84 is one of the most abundant fullerenes and has 24 isomers obeying the isolated pentagon rule (IPR), 21 among which 14 isomers have been already isolated in the form of both empty and endohedral fullerenes, including D 2d (4), D 2 (5), C 2v (7), C 2 (11), C 1 (12), C 2 (13), C s (14), C s (15), C s (16), C 2v (18), D 3d (19), D 2 (22), D 2d (23), and D 6d (24). 22−31 Particularly, according to theoretical calculations, the relative energy of the C 2v (17) isomer is lower than those of several isolated isomers, such as D 2d (4), D 2 (5), C 2v (7), C 2 (13), C s (14), C s (15), C s (16), C 2v (18), D 2 (22), D 2d (23), and D 6d (24) (in either electroneutral or dianion form 32,33 ), thus is expected to be separable.…”

Anomalous Cis‐Conformation Regioselectivity of Heterocycle‐Fused Sc3N@D3h‐C78 Derivatives

“…The soot containing Sc 3 N@ D 3 h ‐C 78 was synthesized by a direct current arc‐discharge method [39] and was extracted with carbon disulfide (CS 2 ). The filtered CS 2 solution was transferred to toluene solution and subjected to multi‐step high performance liquid chromatography (HPLC) separation to obtain pure Sc 3 N@ D 3 h ‐C 78 (Supporting Information, Figure S1).…”