Reversible Size Control of Silver Nanoclusters via Ligand-exchange
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ArticleAuthors
Bootharaju, Megalamane Siddaramappa
Burlakov, Victor M.
Besong, Tabot M.D.

Joshi, Chakra Prasad
Reshi, Owais A.

Black, David
Whetten, Robert
Goriely, Alain

Bakr, Osman

KAUST Department
Functional Nanomaterials Lab (FuNL)KAUST Catalysis Center (KCC)
KAUST Solar Center (KSC)
Material Science and Engineering Program
Physical Science and Engineering (PSE) Division
Date
2015-06-05Online Publication Date
2015-06-05Print Publication Date
2015-06-23Permanent link to this record
http://hdl.handle.net/10754/555643
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The properties of atomically monodisperse noble metal nanoclusters (NCs) are intricately intertwined with their precise molecular formula. The vast majority of size-specific NC syntheses start from the reduction of the metal salt and thiol ligand mixture. Only in gold was it recently shown that ligand-exchange could induce the growth of NCs from one atomically precise species to another; a process of yet unknown reversibility. Here, we present a process for the ligand-exchange-induced growth of atomically precise silver NCs, in a biphasic liquid-liquid system, which is particularly of interest because of its complete reversibility and ability to occur at room temperature. We explore this phenomenon in-depth using Ag35(SG)18 [SG= glutathionate] and Ag44(4-FTP)30 [4-FTP= 4-fluorothiophenol] as model systems. We show that the ligand-exchange conversion of Ag35(SG)18 into Ag44(4-FTP)30 is rapid (< 5 min) and direct, while the reverse process proceeds slowly through intermediate cluster sizes. We adapt a recently developed theory of reverse Ostwald ripening to model the NCs’ interconvertibility. The model’s predictions are in good agreement with the experimental observations, and they highlight the importance of small changes in the ligand-metal binding energy in determining the final equilibrium NC size. Based on the insight provided by this model, we demonstrated experimentally that by varying the choice of ligands, ligand-exchange can be used to obtain different sized NCs. The findings in this work establish ligand-exchange as a versatile tool for tuning cluster sizes.Citation
Reversible Size Control of Silver Nanoclusters via Ligand-exchange 2015:150521100629001 Chemistry of MaterialsPublisher
American Chemical Society (ACS)Journal
Chemistry of MaterialsAdditional Links
http://pubs.acs.org/doi/abs/10.1021/acs.chemmater.5b00650ae974a485f413a2113503eed53cd6c53
10.1021/acs.chemmater.5b00650