A Cut-to-Link Strategy for Cubane-Based Heterometallic Sulfide Clusters with Giant Third-Order Nonlinear Optical Response
Zhi-Kang Wang 1, 2 , Ming-Hao Du 1*（杜明浩） , Pierre Braunstein 3 , Jian-Ping Lang 1, 2*（郎建平）
1 College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123, China.
2 State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.
3 Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 67081 Strasbourg, France.
J. Am. Chem. Soc. 2023, 145, 9982--9987
Although the synthesis of low-dimensional metal sulfides by assembling cluster-based units is expected to promote the development of optical materials and models of enzyme active centers such as dinitrogenase, it is faced with limited assembly methodology. Herein we present a cut-to-link strategy to generate high-nuclearity assemblies, inspired by the formation of a Z-type dimer of the W−S−Cu analogues of PN cluster through in situ release of active linkers. Four new compounds with structures based on the same {Tp*WS3Cu3} incomplete cubane-like units were obtained using varied combinations of mild reagents. Open-aperture Z-scan measurements demonstrated the highest-nuclearity complex has the largest nonlinear optical absorption coefficient among discrete cluster-based materials reported to date. This approach enables building high-nuclearity metal sulfide clusters through cluster-based building blocks and opens a way to the design and exploration of materials based on well-identified building blocks.
链接：//pubs.acs.org/doi/full/10.1021/jacs.3c01831
