Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, Ibaraki 305-8577, Japan.
Chem Rec. 2012 Apr;12(2):256-69. doi: 10.1002/tcr.201100038. Epub 2012 Apr 10.
This account presents an overview of our achievements in structural and chemical understanding of endohedral metallofullerenes (EMFs), a new class of metal-carbon hybrid materials formed by encapsulation of metals inside fullerene cavities. Structural determination of EMFs is of fundamental importance for understanding their intrinsic properties and the formation mechanism, and for broadening their applications. We have developed an effective method for determining the structures of paramagnetic EMFs, and also succeeded in observing the motion of cluster in a di-metal EMF for the first time. Recently, we unambiguously established the structures of some carbide EMFs which had been wrongly assumed as conventional EMFs previously. More importantly, we have obtained some insoluble EMF species which had never been explored or even expected before. Meanwhile, the chemical properties of various EMFs with different cage structures or different metallic cores have been systematically investigated by means of both covalent and supramolecular considerations, yielding many fascinating results relating to the dictating effect of internal metals. It is noteworthy that all these achievements are based on unambiguous X-ray results of pristine or functionalized EMFs.
本报告概述了我们在金属富勒烯（EMF）的结构和化学理解方面的成就，金属富勒烯是一类新型的金属-碳杂化材料，由金属封装在富勒烯腔体内形成。EMF 的结构确定对于理解其内在性质和形成机制以及拓宽其应用具有重要意义。我们已经开发出一种有效确定顺磁 EMF 结构的方法，并首次成功观察到双金属 EMF 中团簇的运动。最近，我们明确确定了一些之前被错误认为是常规 EMF 的碳化物 EMF 的结构。更重要的是，我们获得了一些以前从未探索过甚至未曾预料到的不溶性 EMF 物质。同时，通过共价和超分子考虑，系统研究了具有不同笼状结构或不同金属核的各种 EMF 的化学性质，得到了许多与内部金属的控制作用有关的迷人结果。值得注意的是，所有这些成就都是基于原始或功能化 EMF 的明确 X 射线结果。
