摘要
The design and synthesis of artificial molecular switches (AMSs) displaying architectures of increased complexity would constitute significant progress in meeting the challenging task of realizing artificial molecular machines (AMMs). Here, we report the synthesis and characterization of a molecular shuttle composed of a cyclobis(paraquat-4,4′-biphenylene) cyclophane ring and a dumbbell incorporating a cyclobis(paraquat-m-phenylene) cyclophane “head” and a bifurcated, tawse-like “tail” composed of two oligoether chains, each containing a 1,5-dioxynaphthalene ring. In its reduced state the ring-in-ring recognition motif, between the meta and para bisradical dicationic cyclophanes (rings), defines the [2]rotaxane, whereas in the oxidized state, the cyclobis(paraquat-4,4′-biphenylene) cyclophane encircles the two 1,5-dioxynaphthalene rings in the bifurcated “tail”. The redox-controlled molecular shuttling, which can be likened to the action of a zipper in the macroscopic world, exhibits slow kinetics dampened by
摘要译文
显示复杂性不断增加的体系结构的人工分子开关（AMS）的设计与合成将在满足实现人工分子机器（AMM）的艰巨任务方面取得重大进展。在这里，我们报告由环双（百草枯-4,4'-联苯）环庚烯环和结合了环双（百草枯-间苯撑）环庚烯“头”和分叉的桃花芯的哑铃组成的分子穿梭的合成和表征由两个寡醚链组成的“尾巴”，每个都包含一个1,5-二氧萘环。在还原状态下，间和对双基双价双环基环（环）之间的环内环识别基序定义了[2]轮烷，而在氧化态下，环双（百草枯-4,4'-联苯）环烷环绕着分叉的“尾巴”中的两个1,5-二氧萘环。氧化还原控制的分子穿梭，可以比作宏观世界中拉链的作用，表现出缓慢的动力学受阻尼
Melissa Dumartin [1];Mark C. Lipke[*] [2];J. Fraser Stoddart[*] [1]. A Redox-Switchable Molecular Zipper[J]. Journal of the American Chemical Society, 2019,141(45): 18308-18317