The Covalent and Coordination Co-Driven Assembly of Supramolecular Octahedral Cages with Controllable Degree of Distortion
Shu-Jin Bao1,2, Ze-Ming Xu1, Yun Ju3, Ying-Lin Song3, Heng Wang4, Zheng Niu1,*（牛政）, Xiaopeng Li4, Pierre Braunstein5, and Jian-Ping Lang1,2,*（郎建平）
1 College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, Jiangsu, China
2 State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
3 School of Physical Science and Technology, Soochow University, Suzhou 215006, Jiangsu, China
4 Chemistry Department, University of South Florida, Tampa, Florida 33620, United States
5 Institut de Chimie (UMR 7177 CNRS), Universitéde Strasbourg, 67081 Strasbourg, France
J. Am. Chem. Soc.2020, 142, 13356--13361
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.
链接：https://pubs.acs.org/doi/10.1021/jacs.0c07014