Yan Xing-Xing, Li Bairu, Lin Hao-Sheng, Jin Fei, Niu Chuang, Liu Kai-Qing, Wang Guan-Wu, Yang Shangfeng
Hefei National Laboratory for Physical Sciences at Microscale, CAS Key Laboratory of Soft Matter Chemistry, Center for Excellence in Molecular Synthesis of CAS, and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China.
Hefei National Laboratory for Physical Sciences at Microscale, CAS Key Laboratory of Materials for Energy Conversion, and Department of Materials Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026, China.
Research (Wash D C). 2020 Feb 15;2020:2059190. doi: 10.34133/2020/2059190. eCollection 2020.
With the recent advance in chemical modification of fullerenes, electrosynthesis has demonstrated increasing importance in regioselective synthesis of novel fullerene derivatives. Herein, we report successively regioselective synthesis of stable tetra- and hexafunctionalized [60]fullerene derivatives. The cycloaddition reaction of the electrochemically generated dianions from [60]fulleroindolines with phthaloyl chloride regioselectively affords 1,2,4,17-functionalized [60]fullerene derivatives with two attached ketone groups and a unique addition pattern, where the heterocycle is rearranged to a [5,6]-junction and the carbocycle is fused to an adjacent [6,6]-junction. This addition pattern is in sharp contrast with that of the previously reported biscycloadducts, where both cycles are appended to [6,6]-junctions. The obtained tetrafunctionalized compounds can be successively manipulated to 1,2,3,4,9,10-functionalized [60]fullerene derivatives with an intriguing ""-shaped configuration a novel electrochemical protonation. Importantly, the stability of tetrafunctionalized [60]fullerene products allows them to be applied in planar perovskite solar cells as efficient electron transport layers.
随着富勒烯化学修饰的最新进展，电合成在新型富勒烯衍生物的区域选择性合成中显示出越来越重要的作用。在此，我们相继报道了稳定的四官能化和六官能化[60]富勒烯衍生物的区域选择性合成。[60]富勒烯吲哚啉电化学产生的二价阴离子与邻苯二甲酰氯的环加成反应区域选择性地提供了具有两个连接酮基和独特加成模式的1,2,4,17-官能化[60]富勒烯衍生物，其中杂环重排为[5,6]连接，碳环与相邻的[6,6]连接稠合。这种加成模式与先前报道的双环加合物形成鲜明对比，在双环加合物中两个环都连接到[6,6]连接上。所得到的四官能化化合物可以相继转化为具有有趣的“-”形构型的1,2,3,4,9,10-官能化[60]富勒烯衍生物——一种新型的电化学质子化反应。重要的是，四官能化[60]富勒烯产物的稳定性使其能够作为高效电子传输层应用于平面钙钛矿太阳能电池中。
