The Covalent and Coordination Co-Driven Assembly of Supramolecular Octahedral Cages with Controllable Degree of Distortion

Shu-Jin Bao, Ze-Ming Xu, Yun Ju, Ying-Lin Song, Heng Wang, Zheng Niu, Xiaopeng Li, Pierre Braunstein, Jian-Ping Lang

Discovering and constructing novel and fancy structures is the goal of many supramolecular chemists. In this work, we propose an assembly strategy based on the synergistic effect of coordination and covalent interactions to construct a set of octahedral supramolecular cages and adjust their degree of distortion. Our strategy innovatively utilizes the addition of sulfur atoms of a metal sulfide synthon, [Et4N][Tp*WS3] (A), to an alkynyl group of a pyridine-containing linker, resulting in a novel vertex with low symmetry, and of Cu(I) ions. By adjusting the length of the linker and the position of the reactive alkynyl group, the control of the deformation degree of the octahedral cages can be realized. These supramolecular cages exhibit enhanced third-order nonlinear optical (NLO) responses. The results offer a powerful strategy to construct novel distorted cage structures as well as control the degree of distortion of supramolecular geometries.

具有可控畸变度的超分子八面体笼的共价和配位共驱动组装

发现和构建新颖奇特的结构是许多超分子化学家的目标。在这项工作中，我们提出了一种基于协调和共价相互作用协同效应的组装策略，以构建一组八面体超分子笼并调整它们的变形程度。我们的策略创新性地利用金属硫化物合成子 [Et4N][Tp*WS3] (A) 的硫原子添加到含吡啶连接体的炔基上，从而产生具有低对称性的新型顶点，以及 Cu （一）离子。通过调节接头的长度和反应性炔基的位置，可以实现八面体笼形变程度的控制。这些超分子笼表现出增强的三阶非线性光学 (NLO) 响应。

jacs.0c07014.pdf