Threefold Collaborative Stabilization of Ag₁₄‐Nanorods by Hydrophobic Ti₁₆‐Oxo Clusters and Alkynes: Designable Assembly and Solid‐State Optical‐Limiting Application

Abstract

Ag nanoclusters have received increasing attention due to their atomically precise and diverse structures and intriguing optical properties. Nevertheless, the inherent instability of Ag nanoclusters has seriously hindered their practical application. In this work, for the first time, Ag clusters are collaboratively protected by hydrophobic Ti-oxo clusters and alkyne ligands. Initially, a pyramidal Ag₅ cluster terminated with ^t BuC≡C^- and CH₃ CN was inserted into the cavity of a Ti₈ -oxo nanoring to form Ag₅ @Ti₈ . To overcome the instability of acetonitrile-terminated silver site, such two Ag₅ @Ti₈ clusters could sandwich an Ag₄ unit to form Ag₁₄ -nanorod@Ti₁₆ -oxo-nanoring (Ag₁₄ @Ti₁₆ ), which is peripherally protected by fluorophenyl groups and alkyne caps. This threefold protected (hydrophobic fluorinated organic layer, Ti-O shell, and terminal alkyne ligands) Ag₁₄ @Ti₁₆ exhibits superhydrophobicity and excellent ambient stability, endowing it with solid-state optical limiting characteristics.