Yang Linlin, Jing Xu, An Bowen, He Cheng, Yang Yang, Duan Chunying
State Key Laboratory of Fine Chemicals , College of Zhang Dayu , Dalian University of Technology , Dalian , 116024 , P. R. China . Email:
Chem Sci. 2017 Nov 30;9(4):1050-1057. doi: 10.1039/c7sc04070a. eCollection 2018 Jan 28.
By synergistic combination of multicomponent self-assembly and template-directed approaches, triply interlocked metal organic catenanes that consist of two isolated chirally identical tetrahedrons were constructed and stabilized as thermodynamic minima. In the presence of suitable template anions, the structural conversion from the isolated tetrahedral conformers into locked catenanes occurred the cleavage of an intrinsically reversible coordination bond in each of the tetrahedrons, followed by the reengineering and interlocking of two fragments with the regeneration of the broken coordination bonds. The presence of several kinds of individual pocket that were attributed to the triply interlocked patterns enabled the possibility of encapsulating different anions, allowing the dynamic allostery between the unlocked/locked conformers to promote the dehalogenation reaction of 3-bromo-cyclohexene efficiently, as with the use of dehalogenase enzymes. The interlocked structures could be unlocked into two individual tetrahedrons through removal of the well-matched anion templates. The stability and reversibility of the locked/unlocked structures were further confirmed by the catching/releasing process that accompanied emission switching, providing opportunities for the system to be a dynamic molecular logic system.
通过多组分自组装和模板导向方法的协同结合，构建了由两个孤立的手性相同四面体组成的三重互锁金属有机索烃，并将其稳定为热力学最小值。在合适的模板阴离子存在下，从孤立的四面体构象体到锁定索烃的结构转变发生在每个四面体中固有的可逆配位键断裂之后，随后是两个片段的重新构建和互锁以及断裂配位键的再生。归因于三重互锁模式的几种不同的个体口袋的存在使得封装不同阴离子成为可能，从而使未锁定/锁定构象体之间的动态变构能够像使用脱卤酶一样有效地促进3-溴环己烯的脱卤反应。通过去除匹配良好的阴离子模板，互锁结构可以解锁为两个单独的四面体。锁定/解锁结构的稳定性和可逆性通过伴随发射切换的捕获/释放过程得到进一步证实，为该系统成为动态分子逻辑系统提供了机会。
