Abstract：
Self-sorting is commonly observed in complex reaction systems, which has been utilized to guide the formation of single major by-design molecules. However, most studies have been focused on non-covalent systems, and using self-sorting to achieve covalently bonded architectures is still relatively less explored. Herein, we first demonstrated the dynamic nature of spiroborate linkage and systematically studied the self-sorting behavior observed in the transformation between spiroborate-linked well-defined polymeric and molecular architectures, which is enabled by spiroborate bond exchange. The scrambling between a macrocycle and a 1D helical covalent polymer led to the formation of a molecular cage, whose structures are all unambiguously elucidated by single-crystal X-ray diffraction. The results indicate that the molecular cage is the thermodynamically favored product in this multi-component reaction system. This work represents the first example of a 1D polymeric architecture transforming into a shape-persistent molecular cage, driven by dynamic covalent self-sorting. This study will further guide the design of spiroborate-based materials and open the possibilities for the development of novel complex yet responsive dynamic covalent molecular or polymeric systems.
摘要：
在复杂的反应系统中通常观察到自分选，它已被用来指导单一主要设计分子的形成。然而,大多数研究都集中在非共价系统上，和使用自分类来实现共价键合的结构仍然相对较少的探索。在这项工作中,我们首先证明了螺硼酸盐连接的动态性质，并系统地研究了在螺硼酸盐连接的明确聚合物和分子结构之间的转化中观察到的自分选行为，这是通过螺硼酸盐键交换实现的。大环和一维螺旋共价聚合物之间的混乱导致分子笼的形成，其结构均通过单晶X射线衍射明确阐明。结果表明，在这种多组分反应体系中，分子笼是热力学上有利的产物。这项工作代表了一维聚合物结构转变为形状持久的分子笼的第一个例子，由动态共价自分选驱动。这项研究将进一步指导螺硼酸盐基材料的设计，并为开发新的复杂而响应的动态共价分子或聚合物系统开辟可能性。
