Lorenz Patrick, Wullschläger Florian, Rüter Antonia, Meyer Bernd, Hirsch Andreas
Chair of Organic Chemistry II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nikolaus-Fiebiger-Str. 10, 91058, Erlangen, Germany.
Interdisciplinary Center for Molecular Materials (ICMM) and, Computer Chemistry Center (CCC), Friedrich-Alexander-Universität Erlangen-Nürnberg, Nägelsbachstr. 25, 91052, Erlangen, Germany.
Chemistry. 2021 Oct 19;27(58):14501-14507. doi: 10.1002/chem.202102109. Epub 2021 Sep 16.
With respect to molecular switches, initializing the quadricyclane (QC) to norbornadiene (NBD) back-reaction by light is highly desirable. Our previous publication provided a unique solution for this purpose by utilizing covalently bound C . In this work, the fundamental processes within these hybrids has been investigated. Variation of the linker unit connecting the NBD/QC moiety with the fullerene core is used as a tool to tune the properties of the resulting hybrids. Utilizing the Prato reaction, two unprecedented NBD/QC - fullerene hybrids having a long-rigid and a short-rigid linker were synthesized. Molecular dynamics simulations revealed that this results in an average QC-C distance of up to 14.2 Å. By comparing the NBD-QC switching of these derivatives with the already established one having a flexible linker, valuable mechanistic insights were gained. Most importantly, spatial convergence of the QC moiety and the fullerene core is inevitable for an efficient back-reaction.
关于分子开关，通过光照使四环烷（QC）向降冰片二烯（NBD）的逆反应初始化是非常理想的。我们之前的出版物通过利用共价连接的C为此提供了一个独特的解决方案。在这项工作中，对这些杂化物中的基本过程进行了研究。连接NBD/QC部分与富勒烯核心的连接单元的变化被用作调整所得杂化物性质的工具。利用普拉托反应，合成了两种具有长刚性和短刚性连接基的前所未有的NBD/QC - 富勒烯杂化物。分子动力学模拟表明，这导致QC-C的平均距离高达14.2 Å。通过将这些衍生物的NBD-QC开关与已建立的具有柔性连接基的衍生物进行比较，获得了有价值的机理见解。最重要的是，对于有效的逆反应，QC部分和富勒烯核心的空间收敛是不可避免的。
