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三壳超分子配合物实现了C60的对称性失配的化学和区域选择性双功能化
作者:小柯机器人 发布时间:2021/4/18 20:43:32

西班牙赫罗纳大学Xavi Ribas团队报道了三壳超分子配合物实现了C60的对称性失配的化学和区域选择性双功能化。 相关研究成果发表在在2021年4月15日出版的《自然—化学》。

俄罗斯分子娃娃(俄罗斯套娃)已被证明测试制备超分子化学的极限非常有用,但应用这些架构的问题在其他领域是难以捉摸的。

该文中,研究人员报告了一个三壳的类似俄罗斯套娃的复合物(其中C60位于一个环对苯撑纳米环中,而环对苯撑纳米环又被封装在一个自组装的纳米胶囊中)可以用来解决富勒烯化学中的一个长期挑战,即选择性形成一个特定的富勒烯双加合物。

光谱分析表明,三元络合物在溶液中足够稳定,使两个外壳影响富勒烯客体的加成化学。当络合物在宾格尔环丙烷化条件下进行时,在通常产生十几种产物的反应中观察到单一反式-3富勒烯双加成物的独占形成。这种类似俄罗斯套娃的方法所促进的选择性似乎是一种普遍现象,并且对于具有比异构体混合物更好性能的区域异构体纯C60双加合物的应用是有用的。

附:英文原文

Title: A three-shell supramolecular complex enables the symmetry-mismatched chemo- and regioselective bis-functionalization of C 60

Author: Ernest Ubasart, Oleg Borodin, Carles Fuertes-Espinosa, Youzhi Xu, Cristina Garca-Simn, Laura Gmez, Judith Juanhuix, Felipe Gndara, Inhar Imaz, Daniel Maspoch, Max von Delius, Xavi Ribas

Issue&Volume: 2021-04-15

Abstract: Molecular Russian dolls (matryoshkas) have proven useful for testing the limits of preparative supramolecular chemistry but applications of these architectures to problems in other fields are elusive. Here we report a three-shell, matryoshka-like complex—in which C60 sits inside a cycloparaphenylene nanohoop, which in turn is encapsulated inside a self-assembled nanocapsule—that can be used to address a long-standing challenge in fullerene chemistry, namely the selective formation of a particular fullerene bis-adduct. Spectroscopic evidence indicates that the ternary complex is sufficiently stable in solution for the two outer shells to affect the addition chemistry of the fullerene guest. When the complex is subjected to Bingel cyclopropanation conditions, the exclusive formation of a single trans-3 fullerene bis-adduct was observed in a reaction that typically yields more than a dozen products. The selectivity facilitated by this matryoshka-like approach appears to be a general phenomenon and could be useful for applications where regioisomerically pure C60 bis-adducts have been shown to have superior properties compared with isomer mixtures.

DOI: 10.1038/s41557-021-00658-6

Source: https://www.nature.com/articles/s41557-021-00658-6

 

期刊信息

Nature Chemistry:《自然—化学》,创刊于2009年。隶属于施普林格·自然出版集团,最新IF:21.687
官方网址:https://www.nature.com/nchem/
投稿链接:https://mts-nchem.nature.com/cgi-bin/main.plex