Endohedral Metallofullerenes: New Structures and Unseen Phenomena

Endohedral metallofullerenes (EMFs), namely fullerenes with metallic species encapsulated inside, represent an ideal platform to investigate metal–metal or metal–carbon interactions at the sub‐nanometer scale by means of single‐crystal X‐ray diffraction (XRD) crystallography. Herein, recent progress...

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Bibliographic Details
Published in:Chemistry : a European journal 2020-05, Vol.26 (26), p.5748-5757
Main Authors: Shen, Wangqiang, Hu, Shuaifeng, Lu, Xing
Format: Article
Language:English
Subjects:
Actinides
bonding nature
Cages
Chemistry
Clusters
Crystallography
density functional calculations
Dimerization
endohedral metallofullerenes
Fullerenes
Lanthanides
Matching
Metallofullerenes
Metals
Molecular structure
molecular structures
Oxidation
Valence
X-ray crystallography
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Summary:Endohedral metallofullerenes (EMFs), namely fullerenes with metallic species encapsulated inside, represent an ideal platform to investigate metal–metal or metal–carbon interactions at the sub‐nanometer scale by means of single‐crystal X‐ray diffraction (XRD) crystallography. Herein, recent progress in the identification of new structures and unprecedented properties are discussed according to the categories of monometallofullerenes, dimetallofullerenes, carbide clusterfullerenes, and nitride clusterfullerenes. In particular, the dimerization and the cage‐isomer dependent oxidation state of the inner metal atom are summarized in terms of pristine monometallofullerenes. Metal–metal bonds involving lanthanide–lanthanides or actinide–actinides are discussed based on both experimental and theoretical studies. The cluster–cage matching and/or mutual selections, as well as the rarely seen M=C double bonds, are discovered in M2C2@C2n, U2C@C80, M2TiC@C80, and Ti3C3@C80. Subsequently, the geometries of different M3N clusters in various cages are discussed, revealing size‐matching between the internal M3N cluster and the outer cage induced by the planarity of the cluster. Finally, an outlook regarding the future developments of the molecular structures and applications of EMFs is presented. Endohedral metallofullerenes (EMFs) serve as an ideal platform for the study of otherwise unstable metallic clusters owing to the protection afforded by fullerene cages. Herein, a systematic and comprehensive summary of the recent results of EMFs is presented according to the categories of monometallofullerenes, dimetallofullerenes, carbide clusterfullerenes, and nitride clusterfullerenes.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201905306