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

Abstract

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 superatoms protected by face-capping 1,2-dithiolate-o-carborane (CBHS) ligands, each produced from 1-thiol-o-carborane in crystallization with simultaneous reduction of Ag to Ag. We find that the corner N-donor ligands contribute predominately to the stability and luminescence of the Ag superatom. As the first-formed nanocluster [Ag(CBHS)(CHCN)]·4CHCN (NC-1) with labile vertex-coordinated CHCN ligands is highly unstable, monodendate pyridine ligands were used to replace these CHCN species site-specifically, giving [Ag(CBHS)(pyridine/p-methylpyridine)] (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 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.

Core Modulation of 70‐Nuclei Core‐Shell Silver Nanoclusters

“…The hierarchicalm ulti-shells ilver nanocluster assembly found in SD/Ag70a. solvents of different functionalities in the assembly of silver nanoclusters,a nd have synthesized two novel nanoclusters that invoke the MoO 4 2À template.I nt he absence of DMF, high-level hierarchic-structured yellow crystals of (HNEt 3 ) 3 [Ag 4 S 4 (MoO 4 ) 5 @Ag 66 (tBuC 6 H 4 S) 40 (mbc) 15 (H 2 O) 2 ]( SD/ Ag70b), ac luster of 70 Ag atoms enclosing 5M oO 4 2À ions, was obtained in 3days.I nt he presence of DMF,a dditional dark-red crystals of [Ag 10 @(MoO 4 ) 7 @Ag 60 (tBuC 6 H 4 S) 33 (mbc) 18 (DMF)(H 2 O) 2 ]·DMF·H 2 O( SD/Ag70a) were formed after 10 days,w hich comprise aA g 10 kernel surrounded by aring of 7MoO 4 2À ions,which is wrapped in ashell of 60 Ag atoms and can be represented as [Ag 10 @(MoO 4 ) 7 @Ag 60 ].…”

Observation of Non‐FCC Copper in Alkynyl‐Protected Cu53Nanoclusters

“…[9] The decisive role of ligands on the kernel structure has also been exemplified by various Ag NCs. [10,11] These and other inspiring discoveries in the field are excellent models for analyzing the interaction of ligands with metals and also are the key links for understanding the evolution from single atom to the bulk metal. [12][13][14][15][16][17][18][19][20][21][22][23][24] Despite these great progresses,the pursuit of non-FCC Cu has been unexpectedly sluggish.…”

Core Modulation of 70‐Nuclei Core‐Shell Silver Nanoclusters

“…SD/Ag70a adopts the triclinic PÀ1s pace group and the asymmetric unit contains acomplete cluster with the formula [Ag 10 @(MoO 4 ) 7 @Ag 60 (tBuC 6 H 4 S) 33 (mbc) 18 (DMF)-O) 2 ]·DMF·H 2 O. Theo verall appearance of SD/Ag70a is aw heel with ar adial diameter of 1.87 nm and an axial thickness of 0.72 nm. Theo uter shell of the nanocluster consists of 60 silver atoms and the organic ligands,w hile the remaining 10 silver atoms are located in the interior,anchored within 7equatorial MoO 4 2À ions (Figure 1a,b).…”