Sequence-sorted redox-switchable hetero[3]rotaxanes

作     者：Marius Gaedke Henrik Hupatz Felix Witte Susanne M.Rupf Clara Douglas Hendrik V.Schröder Lukas Fischer Moritz Malischewski Beate Paulus Christoph A.Schalley 

作者机构：Institut für Chemie und Biochemie der Freien Universität BerlinArnimallee 2014195 BerlinGermany Institut für Chemie und Biochemie der Freien Universität BerlinArnimallee 2214195 BerlinGermany Institut für Chemie und Biochemie der Freien Universität BerlinFabeckstr.34/3614195 BerlinGermany 

出 版 物：《Organic Chemistry Frontiers》 (有机化学前沿（英文）)

年 卷 期：2022年第9卷第1期

页      面：64-74页

核心收录：

学科分类：0710[理学-生物学] 081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 0702[理学-物理学] 0812[工学-计算机科学与技术（可授工学、理学学位）] 

基　　金：funding from the Deutsche Forschungsgemeinschaft(DFG project number 434455294) acknowledge the assistance of the Core Facility BioSupraMol supported by the DFG.Furthermore,F.W.and B.P.acknowledge the DFG for funding(PA 1360/16-1) the North-German Supercomputing Alliance(Norddeutscher Verbund für Hoch-und Höchstleistungsrechnen)for providing computational resources 

主　　题：properties redox Sequence 

摘      要：From a library of five crown ether macrocycles with different ring sizes and redox-active moieties,such as tetrathiafulvalene(TTF)and naphthalene dimiide(NDI),directional heterocircuit[3]rotaxanes were *** an axle with two binding sites with different steric accessibility,the concept of integrative self-sorting was applied to program the sequence of functional units in heteropseudo[3]*** on binding strength and ring size of the smaller macrocycles,different heteropseudo[3]rotaxane selectivities and stabilities were determined by 2D NMR spectroscopy and tandem mass spectrometry.A heteropseudo[3]rotaxane with rotaxane-like behaviour was isolated chromatographically,displaying electrochemically“frustratedproperties.A robust synthetic procedure was developed allowing the synthesis of four new hetero[3]rotaxanes incorporating specific sequences of functional *** pseudoisomeric rotaxanes which have the naphthalene diimide subunit at two different positions show distinct electrochemical *** calculations suggest that this differences could arise from a folding of the structure,in which the redox-active moieties stack with a stopper *** study presents a blueprint for the construction of hetero[3]rotaxanes with sequential control of the functional units along the track of the axle and paves the way to extend the functionality of mechanically interlocked molecules.