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.N evertheless,t he inherent instability of Ag nanoclusters has seriously hindered their practical application. In this work, for the first time,A gc lusters are collaboratively protected by hydrophobic Ti-oxo clusters and alkyne ligands.I nitially,apyramidal Ag 5 cluster terminated with t BuCC À and CH 3 CN was inserted into the cavity of aTi 8oxonanoring to form Ag 5 @Ti 8 .T oovercome the instability of acetonitrile-terminated silver site,s uch two Ag 5 @Ti 8 clusters could sandwicha nA g 4 unit to form Ag 14 -nanorod@Ti 16 -oxonanoring (Ag 14 @Ti 16 ), whichi sp eripherally protected by fluorophenyl groups and alkyne caps.This threefold protected (hydrophobic fluorinated organic layer,T i-O shell, and terminal alkyne ligands) Ag 14 @Ti 16 exhibits superhydrophobicity and excellent ambient stability,e ndowing it with solidstate optical limiting characteristics.

Protection of Ag Clusters by Metal‐Oxo Modules

“…Subsequently, to develop more efficient TiÀ O protecting shell for increasing the ambient stability of encapsulated Ag nanoclusters, we groundbreakingly designed the assembly of silver clusters with threefold synergistic stabilization by hydrophobic fluorinated organic layer, TOC shell and alkyne ligands. [46] In this work, in situ formed Ti 8 clusters (Figures 6a and d) were assembled with silver ions and tert-butyl acetylene to form Ag 5 @Ti 8 coreshell nanocluster, whose Ag 5 core was further terminated with t BuC � C À and CH 3 CN (Figures 6b and e). On this basis, the reaction conditions were further adjusted via replacing the acetonitrile solvent with toluene.…”

Array configurations of oxometallate–Ag cluster hybrid nanocomposites

“…13d and e). 54 Ag 14 @Ti 16 represents the first example of Ag clusters synergistically stabilized by alkynyl and Ti-oxo cluster shells. The robust protecting shell of Ag 14 @Ti 16 accounts for its superhydrophobicity and excellent ambient stability.…”

Heterometallic Polyoxotitanium Clusters as Bifunctional Electrocatalysts for Overall Water Splitting

“…Crystalline metal-doped Ti-oxo clusters (M-TOCs), which can be considered as the molecular analogues for the metal-doped TiO 2 nanomaterials, − provide another way to study the structure–property relationship of a TiO 2 -supported catalytic system. So far, a variety of M-TOCs have been reported, with representative clusters such as the Cd-doped {Cd 5 Ti 12 }, Ln-doped {Ln 8 Ti 10 } and Ag–Ti bimetallic clusters {Ag 2 Ti 12 }, {Ag 6 Ti 16 }, {Ag 14 Ti 16 }, and {Ag 10 Ti 28 } . Some clusters exhibit good photocatalytic H 2 evolution capacity − and electrochemical water oxidation performance .…”