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 Ag56 cluster and the carbonate-templated Ag33 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.
Highlights
We report a catalyzed assembly strategy to construct a hollow silver-sulfide cluster, Ag56S12(StBu)20(Sal)[12] (1, HStBu = tert-Butylthiol, H(Sal) = salicylic acid), using a self-releasable anion template. This hollow Ag56 cluster is synthesized from small precursors, whereas a carbonate-templated Ag33 nest-like intermediate is found during the growth of Ag56 cluster
Structures of Ag56 cluster and Ag33 intermediate are characterized by single-crystal X-ray analysis, and the growth kinetics are investigated by time-dependent ultraviolet (UV)–visible (Vis) spectroscopy, revealing the catalyst-like behavior of the self-releasable carbonate template
Cluster 1 was synthesized by adding silver salicylate hydrate (Ag(Sal)·H2O, 1.2 mmol) and AgStBu (4.5 mmol) into a mixture of acetonitrile, dichloromethane, and methanol (v/v = 1:1:1)
Summary
We report a catalyzed assembly strategy to construct a hollow silver-sulfide cluster, Ag56S12(StBu)20(Sal)[12] (1, HStBu = tert-Butylthiol, H(Sal) = salicylic acid), using a self-releasable anion template. This hollow Ag56 cluster is synthesized from small precursors, whereas a carbonate-templated Ag33 nest-like intermediate is found during the growth of Ag56 cluster. Structures of Ag56 cluster and Ag33 intermediate are characterized by single-crystal X-ray analysis, and the growth kinetics are investigated by time-dependent ultraviolet (UV)–visible (Vis) spectroscopy, revealing the catalyst-like behavior of the self-releasable carbonate template
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