Chemically induzed cagetransformations of fullerenes

在KE 489/39-2项目（2015年1月至2018年6月由DFG提交和支持）的过程中，取得了许多成果，这些成果不仅发展了高等富勒烯的化学性质，而且重要的是开辟了非常有前景的前景。由于在实施该项目期间开发的有效和灵敏的方法的应用，在富勒烯化学方面取得了大量显着的成果。这些包括用微量物质进行反应，有效的色谱分离，以及使用同步辐射进行单晶x射线衍射实验。主要成果包括：1)发现了C88、C96、C100、C104、C106和C108等更高阶富勒烯的新异构体，其中C108是迄今为止结构表征最高的富勒烯；2)发现了化学反应过程中新的笼型转化并对其进行了理论处理。新的骨架转变包括富勒烯C100中的新型Stone-Wales重排（SWR2），通过C2损失导致七方体消除的新型笼形收缩，以及C88、C100和C102中的几次多步转变，这些转变产生了非ipr C102和非经典富勒烯的氯化物(C84、C96、C98、和C102),iii)通过氯化产物的三氟甲基化导致形成混合CF3/F衍生物的骨架转化的新鉴定方法（主报告图9）。这意味着一种新型的氟化反应，其途径尚不清楚，iv)我们在骨架转化领域的实验经验，以及对转化机制的理论考虑，使我们最近不仅可以用更高的富勒烯，而且可以用“普通”富勒烯，C60和C70进行这种转化。C60转化的最壮观的结果，在我们的报告中显示在图10中，作为一个令人印象深刻的“神奇分子”的例子，C60Cl20，有五对融合的五边形。因此，首次合成非ipr C60和C70衍生物的显著结果打开了一个新的、非常有趣的研究领域。与更高富勒烯的笼形转化相比，C60和C70的实验可以在制备规模上进行。因此，研究非ipr C60和C70的物理和化学性质应该是可能的。在第一个非常有希望的结果的基础上，现在似乎有必要改变合成和分离条件，以找到获得新化合物的最佳方法，从而使进一步的结构研究成为可能。

In the course of project KE 489/39-2 (submitted and supported by the DFG from January 2015 up to June 2018) many results have been obtained, which the chemistry of higher fullerenes not only develop but, importantly, open highly promising prospects. The large number of remarkable results in the fullerene chemistry were achieved due to the application of effective and sensitive methods which have been developed during carrying out this project. These include performing the reactions with tiny amounts of substances, effective chromatographic separation, and the use of synchrotron radiation for single crystal X-ray diffraction experiments. The main results include i) the discovery of new isomers of higher fullerenes such as C88, C96, C100, C104, C106, and C108, the latter being so far the highest structurally characterized fullerene, ii) the discovery and theoretical treatment of new cage transformations in the course of chemical reactions. The new skeletal transformations include a new type of Stone-Wales rearrangements (SWR2) in fullerene C100, a new type of cage shrinkage via C2 losses which results in heptagon elimination, and several multistep transformations in C88, C100, and C102, which resulted in chlorides of non-IPR C102 as well as non-classical fullerenes (C84, C96, C98, and C102),iii) a new identification method for skeletal transformations via trifluoromethylation of chlorination products which results in the formation of mixed CF3/F derivatives (Fig. 9 in the main report). This implies a new type of fluorination reaction, the pathway of which is still unknown,iv) our experimental experiences in the field of skeletal transformations supported by theoretical considerations of transformation mechanisms allowed us recently to perform such transformations not only with higher but also with “usual” fullerenes, C60 and C70. The most spectacular result of a transformation of C60, is shown in our report in Figure 10 as an impressive example of a “wonder molecule”, C60Cl20, with five pairs of fused pentagons. Therefore, the remarkable results of the first syntheses of non-IPR C60 and C70 derivatives open a new, highly interesting field of research. In contrast to cage transformations in higher fullerenes, the experiments with C60 and C70 can be performed on a preparative scale. It should be therefore possible to investigate physical and chemical properties of non-IPR C60 and C70. On the basis of the first highly promising results, it seems now necessary to vary the synthesis and separation conditions in order to find optimal methods for obtaining new compounds, thus enabling further structural studies.