Self-driven carbon atom implantation into fullerene embedding metal–carbon cluster

• Published in: Proceedings of the National Academy of Sciences - PNAS Vol. 119; no. 39; p. 1
• Main Authors: Guan, Runnan, Chen, Zuo-Chang, Huang, Jing, Tian, Han-Rui, Xin, Jinpeng, Ying, Si-Wei, Chen, Muqing, Zhang, Qianyan, Li, Qunxiang, Xie, Su-Yuan, Zheng, Lan-Sun, Yang, Shangfeng
• Format: Journal Article
• Language: English
• Published: Washington National Academy of Sciences 27-09-2022
• Subjects: Cages; Carbides; Carbon; Chemists; Clusters; Crystallography; Embedding; Fullerenes; Implantation; Ion bombardment; Nuclear weapons; Organometallic complexes; Scandium; Single electrons; Vanadium
• ISSN: 0027-8424; 1091-6490
• DOI: 10.1073/pnas.220256311

Hundreds of members have been synthesized and versatile applications have been promised for endofullerenes (EFs) in the past 30 y. However, the formation mechanism of EFs is still a long-standing puzzle to chemists, especially the mechanism of embedding clusters into charged carbon cages. Here, based on synthesis and structures of two representative vanadium–scandium–carbido/carbide EFs, VSc2C@Ih (7)-C80 and VSc2C2@Ih (7)-C80, a reasonable mechanism-C1 implantation (a carbon atom is implanted into carbon cage)-is proposed to interpret the evolution from VSc2C carbido to VSc2C2 carbide cluster. Supported by theoretical calculations together with crystallographic characterization, the single electron on vanadium (V) in VSc2C@Ih (7)-C80 is proved to facilitate the C1 implantation. While the V=C double bond is identified for VSc2C@Ih (7)-C80, after C1 implantation the distance between V and C atoms in VSc2C2@Ih (7)-C80 falls into the range of single bond lengths as previously shown in typical V-based organometallic complexes. This work exemplifies in situ self-driven implantation of an outer carbon atom into a charged carbon cage, which is different from previous heterogeneous implantation of nonmetal atoms (Group-V or -VIII atoms) driven by high-energy ion bombardment or high-pressure offline, and the proposed C1 implantation mechanism represents a heretofore unknown metal–carbon cluster encapsulation mechanism and can be the fundamental basis for EF family genesis.