A Cut-to-Link Strategy for Cubane-Based Heterometallic Sulfide Clusters with Giant Third-Order Nonlinear Optical Response

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.