Chemically induzed cagetransformations of fullerenes

富勒烯的化学诱导笼形转变

• 批准号: 226393143
• 负责人: Professor Dr. Erhard Kemnitz
• 金额: --
• 依托单位: Institut für Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2012
• 资助国家: 德国
• 起止时间: 2011-12-31 至 2019-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/226393143?language=en
• 关键词: Chemically; induzed; cagetransformations; fullerenes

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.

在KE 489/39-2项目(2015年1月至2018年6月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富勒烯的化学，而且重要的是开辟了非常有前途的前景。在这一项目的实施过程中，由于采用了有效而灵敏的方法，在富勒烯化学中取得了大量显著的成果。这些措施包括与微量物质进行反应，有效的色层分离，以及使用同步辐射进行单晶X射线衍射实验。主要结果包括：1)发现了C88、C96、C100、C104、C106和C108等高富勒烯的新异构体，后者是迄今为止结构特征最高的富勒烯；新的骨架转化包括富勒烯C100中新型的Stone-Wales重排(SWR2)，通过C2损失导致七角形消除的新型笼形收缩，以及C88、C100和C102中的几个多步转化，导致非IPR C102的氯化物以及非经典富勒烯(C84、C96、C98和C102)，iii)通过氯化产物的三氟甲基化反应鉴定骨架转化的新方法，从而形成混合的CF3/F衍生物(主报告中的图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，在转化机制的理论考虑支持下，使我们最近不仅可以用更高的富勒烯，而且还可以用通常的富勒烯、C60和C70进行这种转化。我们在图10中的报告中显示了C60转变的最壮观的结果，它是一个令人印象深刻的“神奇分子”C60Cl20，具有五对融合的五边形。因此，首次合成非IPR C60和C70衍生物的显著结果开启了一个新的、非常有趣的研究领域。与高富勒烯中的笼形转化不同，C60和C70的实验可以在制备规模上进行。因此，应该可以研究非IPR C60和C70的物理和化学性质。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，以便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。