Atomically Precise Site-Specific Tailoring and Directional Assembly of Superatomic Silver Nanoclusters

作者：Zhao‐Yang Wang, Meng-Qi Wang, Yan‐Ling Li, Peng Luo, Tongtong Jia, Ren‐Wu Huang, Shuang‐Quan Zang, Thomas C. W. Mak · 发表于：Journal of the American Chemical Society · 年份：2018 · DOI：10.1021/jacs.7b11338 · 被引用次数：329 · 研究领域：Nanocluster Synthesis and Applications、Pharmacological Effects and Toxicity Studies、Advanced Nanomaterials in Catalysis

Convenient generation of stable superatomic silver clusters and their systematic site-specific tailoring and directional assembly present an enduring and significant challenge. In this work, we prepared a face-centered cubic (fcc) array of Ag 14 superatoms protected by face-capping 1,2-dithiolate- o -carborane (C 2 B 10 H 10 S 2 ) ligands, each produced from 1-thiol- o -carborane in crystallization with simultaneous reduction of Ag + to Ag 0 . We find that the corner N-donor ligands contribute predominately to the stability and luminescence of the Ag 14 superatom. As the first-formed nanocluster [Ag 14 (C 2 B 10 H 10 S 2 ) 6 (CH 3 CN) 8 ]·4CH 3 CN ( NC-1 ) with labile vertex-coordinated CH 3 CN ligands is highly unstable, monodendate pyridine ligands were used to replace these CH 3 CN species site-specifically, giving [Ag 14 (C 2 B 10 H 10 S 2 ) 6 (pyridine/ p -methylpyridine) 8 ] ( NCs-2,3 ) in gram scale with its core structure intact, which features ultrastability up to 150 °C in air. Moreover, using bidentate N-containing ligands to bridge the superatomic Ag 14 building blocks, we constructed an unprecedented hierarchical series of 1D-to-3D superatomic silver cluster-assembled materials ( SCAM-1,2,3,4 ), and SCAM-4 is air-stable up to 220 °C. Furthermore, this series of stable solid-state superatomic-nanocluster materials exhibit tunable dual emission with wide-range thermochromism. The present study constitutes a major step toward the development of ligand-modulation of ...