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Atomically Precise Site-Specific Tailoring and Directional Assembly of Superatomic Silver Nanoclusters
Zhao-Yang Wang1, Meng-Qi Wang1, Yan-Ling Li1
1College of Chemistry and Molecular Engineering, Zhengzhou University , Zhengzhou 450001, China.
Journal of the American Chemical Society
|January 4, 2018
Summary
Researchers developed stable superatomic silver clusters (Ag14) using novel ligands. These clusters can be precisely assembled into advanced materials with tunable dual emission and thermochromism, enhancing stability and functionality.
Area of Science:
- Materials Science
- Nanotechnology
- Inorganic Chemistry
Background:
- Generating stable superatomic silver clusters and controlling their assembly is a significant challenge.
- Existing methods often lack control over site-specific tailoring and directional assembly.
- Superatomic clusters offer unique properties but require robust ligand protection for stability.
Purpose of the Study:
- To develop a convenient method for generating stable superatomic silver clusters (Ag14).
- To achieve site-specific tailoring and directional assembly of these clusters into advanced materials.
- To investigate the influence of ligands on cluster stability, assembly, and optical properties.
Main Methods:
- Preparation of face-centered cubic (fcc) Ag14 superatoms protected by 1,2-dithiolate-o-carborane ligands.
- Simultaneous reduction of Ag+ to Ag0 during crystallization.
- Site-specific ligand exchange using pyridine-based ligands and bridging ligands for assembly.
- Characterization of cluster stability, structure, and optical properties (luminescence, thermochromism).
Main Results:
- Successfully synthesized ultrastable Ag14 superatoms (up to 150 °C in air) using dithiolate-o-carborane and pyridine ligands.
- Constructed hierarchical 1D-to-3D superatomic cluster-assembled materials (SCAMs) with enhanced air stability (up to 220 °C for SCAM-4).
- Observed tunable dual emission and wide-range thermochromism in the assembled materials.
- Demonstrated the predominant role of corner N-donor ligands in enhancing stability and luminescence.
Conclusions:
- This study presents a major advancement in the controlled synthesis and assembly of superatomic silver nanoclusters.
- Ligand modulation is a powerful strategy for enhancing the stability, structural control, and functionality of these materials.
- The developed superatomic silver cluster-assembled materials exhibit promising properties for advanced applications.
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