Wang Dan-Ning, Shen Wangqiang, Li Mengyang, Zhang Mengmeng, Mu Jiuke, Cai Wenting
School of Chemistry, Xi'an Jiaotong University, Xi'an 710049, China.
School of Materials Science and Engineering, Hefei University of Technology, Hefei 230009, China.
Chem Commun (Camb). 2024 Dec 10;60(99):14733-14749. doi: 10.1039/d4cc04341c.
Since the discovery of La@C, a wide array of endohedral metallofullerenes (EMFs) have been synthesized and documented. Various metals, including lanthanides, transition metals, alkali metals, alkaline earth metals and actinides, have been successfully incorporated into the inert fullerene cavities. The interaction between these encapsulated metal species and the fullerene cage isomers plays a crucial role in determining distinct molecular structures and imparting versatile chemical behaviors to these compounds. In particular, recent advancements in EMFs with medium-sized carbon cages, which are among the most versatile categories of EMFs, have marked a significant breakthrough in fundamental coordination chemistry and opened up a wide range of potential applications. The formation of various abnormal metal clusters, possessing unique chemical bonding character and geometric conformations, has been shown to be influenced by novel electron transfer mechanisms between the metal atoms and the carbon cage. Moreover, these specialized metal-cage interactions have also facilitated the stabilization of giant fullerene families and promoted the exploration of these structures in greater detail, particularly with respect to the unanticipated metallofullertubes. Therefore, this review aims to highlight the new phenomena arising from these novel metal-cage interactions in the fundamental study of pristine EMFs. On this basis, we also discussed innovative applications of EMF-based supramolecular complexes that stem from their unique host-guest association.
自从发现La@C以来，已经合成并记录了各种各样的内嵌金属富勒烯（EMF）。包括镧系元素、过渡金属、碱金属、碱土金属和锕系元素在内的各种金属已成功地被纳入惰性富勒烯空腔中。这些被封装的金属物种与富勒烯笼异构体之间的相互作用在决定独特的分子结构以及赋予这些化合物多样的化学行为方面起着至关重要的作用。特别是，中等尺寸碳笼的EMF（这是最具多样性的EMF类别之一）的最新进展在基础配位化学方面取得了重大突破，并开辟了广泛的潜在应用。已表明，具有独特化学键特征和几何构象的各种异常金属簇的形成受到金属原子与碳笼之间新型电子转移机制的影响。此外，这些特殊的金属-笼相互作用还促进了巨型富勒烯家族的稳定，并推动了对这些结构更详细的探索，特别是关于意外的金属富勒烯管。因此，本综述旨在突出这些新型金属-笼相互作用在原始EMF基础研究中产生的新现象。在此基础上，我们还讨论了基于EMF的超分子复合物因其独特的主客体关联而产生的创新应用。
