%0 Generic
%A Wang, Zhao-Yang
%A Wang, Meng-Qi
%A Li, Yan-Ling
%A Luo, Peng
%A Jia, Tong-Tong
%A Huang, Ren-Wu
%A Zang, Shuang-Quan
%A C. W. Mak, Thomas
%D 2018
%T Atomically
Precise Site-Specific Tailoring and Directional
Assembly of Superatomic Silver Nanoclusters
%U https://acs.figshare.com/articles/dataset/Atomically_Precise_Site-Specific_Tailoring_and_Directional_Assembly_of_Superatomic_Silver_Nanoclusters/5774355
%R 10.1021/jacs.7b11338.s005
%2 https://ndownloader.figshare.com/files/10186236
%K superatomic Ag 14 building blocks
%K superatomic-nanocluster materials exhibit tunable
%K CH 3 CN species site-specifically
%K 1 D-to -3D superatomic silver cluster-assembled materials
%K Superatomic Silver Nanoclusters Convenient generation
%K superatomic silver clusters
%K bidentate N-containing ligands
%K monodendate pyridine ligands
%K Ag 14
%K C 2 B 10 H 10 S 2
%K CH 3 CN
%K NC
%K corner N-donor ligands
%K Ag 14 superatoms
%K SCAM
%K vertex-coordinated CH 3 CN ligands
%K superatomic silver nanoclusters
%K Ag 14 superatom
%X 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 Ag14 superatoms protected
by face-capping 1,2-dithiolate-o-carborane (C2B10H10S2) ligands, each produced
from 1-thiol-o-carborane in crystallization with
simultaneous reduction of Ag+ to Ag0. We find
that the corner N-donor ligands contribute predominately to the stability
and luminescence of the Ag14 superatom. As the first-formed
nanocluster [Ag14(C2B10H10S2)6(CH3CN)8]·4CH3CN (NC-1) with labile vertex-coordinated CH3CN ligands is highly unstable, monodendate pyridine ligands
were used to replace these CH3CN species site-specifically,
giving [Ag14(C2B10H10S2)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 Ag14 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 the structure, stability,
assembly, and functionality of superatomic silver nanoclusters.
%I ACS Publications