Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 23, Pages 12949-12954Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202101664
Keywords
cluster compounds; core– shell structures; optical limiting; silver; titanium-oxo clusters
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Funding
- National Natural Science Foundation of China [21922111, 21971038, 22005054]
- Strategic Priority Research Program of the Chinese Academy of Sciences [XDB20000000]
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In this study, Ag clusters were collaboratively protected by hydrophobic Ti-oxo clusters and alkyne ligands, overcoming their inherent instability. This threefold protection resulted in superhydrophobicity and excellent ambient stability of the Ag nanoclusters, leading to solid-state optical limiting characteristics.
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 Ag-5 cluster terminated with (BuC)-Bu-t equivalent to C- and CH3CN was inserted into the cavity of a Ti-8-oxo nanoring to form Ag-5@Ti-8. To overcome the instability of acetonitrile-terminated silver site, such two Ag-5@Ti-8 clusters could sandwich an Ag-4 unit to form Ag-14-nanorod@Ti-16-oxo-nanoring (Ag-14@Ti-16), which is peripherally protected by fluorophenyl groups and alkyne caps. This threefold protected (hydrophobic fluorinated organic layer, Ti-O shell, and terminal alkyne ligands) Ag-14@Ti-16 exhibits superhydrophobicity and excellent ambient stability, endowing it with solid-state optical limiting characteristics.
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