Catalyzed assembly of hollow silver-sulfide cluster through self-releasable anion template

Abstract

Hollow nanoclusters are intriguing for bridging the gap between small metal-organic cages and hollow nanoparticles and provide enormous opportunities for functional materials. Rational construction of hollow nanoclusters remains a challenge owing to the poor understanding of their formation pathways and difficulties in obtaining the intermediate structures. Here we report a catalyzed assembly strategy to construct hollow silver-sulfide clusters using a self-releasable carbonate template. The hollow Ag 56 cluster and the carbonate-templated Ag 33 intermediate are characterized by single-crystal X-ray analysis. Combining this data with a time-dependent UV-Vis spectroscopic investigation, we reveal the catalyst-like behavior of the self-releasable carbonate template and propose the corresponding mechanism. The assembly of hollow clusters using a self-releasable template may provide insight into understanding the formation mechanisms of other hollow nanoclusters and facilitate the design and construction of new hollow nanoclusters.

Synthesis of Two Neutral Silver Alkynyl Nanoclusters by a Single Divalent Tetrahedral Anion Template and a Study of Their Optical Features

“…In addition, template molecules may result in acceleration of the synthesis process, act only as an intermediary, and not appear in the final cluster structure. 14,15 Cationic and neutral templates have often been applied in cluster synthesis, and clusters containing anionic templates have been much less developed. 16 Simple anions appear to form low-nuclearity silver clusters (Ag n , n < 30), and polyoxometals (POMs) are suitable for the preparation of silver clusters with a higher number of nuclei (Ag n , n > 30).…”

“…Metal–metal interaction occurs easily in metal atoms with low oxidation state and large d orbitals, and this kind of interaction is often seen in gold­(I) and silver­(I) compounds. − The synthesis control of silver clusters is a complicated task, and exploring an appropriate and easy method for assembling silver clusters is of great importance. − Structural units containing a metal skeleton, surface organic ligands, and template molecules play a decisive role in the structure of clusters. − Template molecules influence the number of nuclei, size, and geometry of clusters; they help to balance the positive charge and stabilize clusters. In addition, template molecules may result in acceleration of the synthesis process, act only as an intermediary, and not appear in the final cluster structure. , …”

Hexavalent Octahedral Template: A Neutral High-Nucleus Silver Alkynyl Nanocluster Emitting Infrared Light

“…It has been proven that the formation of high-nucleus clusters is facilitated by using an anion template especially oxyanions. − A template molecule can not only determine the size and structure but also be a stabilizer agent of the cluster. In addition, the template may provide additional fruitful properties in the cluster. , The template may act as an accelerator of the synthesis reaction and exist only in the intermediate and not in the final cluster structure . The templates as multiple anions and heteroanions have also been reported to synthesize silver clusters …”

“…13,19 The template may act as an accelerator of the synthesis reaction and exist only in the intermediate and not in the final cluster structure. 20 The templates as multiple anions and heteroanions have also been reported to synthesize silver clusters. 21 In this work, TeO 6 6− as a template was applied to construct a silver nanocluster, for the first time.…”