Fan Xi, Yuan Furong, Li Dejing, Chen Shuai, Cheng Zhibin, Zhang Zhangjing, Xiang Shengchang, Zang Shuang-Quan, Zhang Jian, Zhang Lei
Fujian Provincial Key Laboratory of Polymer Materials, College of Chemistry and Materials Science, Fujian Normal University, 32 Shangsan Road, Fuzhou, 350007, P. R. China.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002, Fuzhou, P. R. China.
Angew Chem Int Ed Engl. 2021 Jun 1;60(23):12949-12954. doi: 10.1002/anie.202101664. Epub 2021 Apr 28.
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 cluster terminated with BuC≡C and CH CN was inserted into the cavity of a Ti -oxo nanoring to form Ag @Ti . To overcome the instability of acetonitrile-terminated silver site, such two Ag @Ti clusters could sandwich an Ag unit to form Ag -nanorod@Ti -oxo-nanoring (Ag @Ti ), 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 @Ti exhibits superhydrophobicity and excellent ambient stability, endowing it with solid-state optical limiting characteristics.
由于其原子精确且多样的结构以及引人入胜的光学性质，银纳米团簇受到了越来越多的关注。然而，银纳米团簇固有的不稳定性严重阻碍了它们的实际应用。在这项工作中，首次通过疏水的钛氧簇和炔烃配体协同保护银团簇。最初，一个以BuC≡C和CH CN封端的金字塔形银团簇被插入到一个钛氧纳米环的腔内形成Ag@Ti。为了克服乙腈封端银位点的不稳定性，这样的两个Ag@Ti团簇可以夹着一个Ag单元形成Ag -纳米棒@Ti -氧代纳米环（Ag@Ti），其外围由氟苯基和炔烃帽保护。这种三重保护（疏水氟化有机层、Ti - O壳和末端炔烃配体）的Ag@Ti表现出超疏水性和优异的环境稳定性，赋予其固态光学限幅特性。
