Dual-ligand modulated Lego-like supracluster assembly of Ti-In-oxo clusters and Ag-P clusters for optical limiting applications
摘要
Supracluster assembly facilitates directional structural control and tailored functional customization of materials, while offering fundamental insights into their structure-property relationships, highlighting both academic significance and application potential. This study presents four novel supraclusters (InOC-24 to InOC-27) synthesized via an innovative dual-ligand strategy: salicylate derivatives stabilize Ti-In-oxo clusters, while bis(diphenylphosphine) ligands stabilize AgP clusters. Their atomically precise and Lego-like modular integration into distinct Ti-In-Ag-based supraclusters is governed by a synergistic interplay of noncovalent interactions, including π-π stacking, electrostatic forces, coordination bonds, and hydrogen bonds. The incorporation of π-conjugated ligands and heavy-metal atoms, coupled with narrow bandgaps arising from ligand-to-metal charge transfer (LMCT) between salicylate derivatives and Ti4+ centers, endows InOC-24 to InOC-27 with exceptional optical limiting (OL) performance, surpassing most reported metal-cluster-based OL materials. These findings highlight their potential application in the field of nonlinear optical (NLO). This work not only presents the first atomically precise ternary-metal (Ti-In-Ag) supraclusters for NLO applications but also establishes a clear “ligand regulation-supracluster assembly-OL modulation” structure-property relationship, offering a new paradigm for designing high-performance nonlinear optical materials.