Title: Interactions between Ultrastable Na₄Ag₄₄(SR)₃₀ Nanoclusters and Coordinating Solvents: Uncovering the Atomic-Scale Mechanism

Abstract

Recently, silver nanoclusters have garnered considerable attention after the high-yield synthesis and crystallization of a thiolate-protected silver nanocluster, Na₄Ag₄₄(SR)₃₀ (SR, protecting thiolate ligand). One intriguing feature of Na₄Ag₄₄(SR)₃₀ is its outstanding stability and resistance to chemical reactions, in striking difference from other silver nanostructures whose susceptibility to oxidation (tarnishing) has been commonly observed and thus limits their applications in nanotechnology. Herein, we report the mechanism on the ultrahigh stability of Na₄Ag₄₄(SR)₃₀ by uncovering how coordinating solvents interact with the Na₄Ag₄₄(SR)₃₀ nanocluster at the atomic scale. Furthermore, through synchrotron X-ray experiments and theoretical calculations, it was found that strongly coordinating aprotic solvents interact with surface Ag atoms, particularly between ligand bundles, which compresses the Ag core and relaxes surface metal–ligand interactions. Furthermore, water was used as a cosolvent to demonstrate that semiaqueous conditions play an important role in protecting exposed surface regions and can further influence the local structure of the silver nanocluster itself. Notably, under semiaqueous conditions, aprotic coordinating solvent molecules preferentially remain on the metal surface while water molecules interact with ligands, and ligand bundling persisted across the varied solvation conditions. This work offers an atomic level mechanism on the ultrahigh stability of the Na₄Ag₄₄(SR)₃₀ nanoclusters from the nanocluster-coordinatingmore » solvent interaction perspective, and implies that nanocluster-solvent interactions should be carefully considered moving forward for silver nanoclusters, as they can influence the electronic/chemical properties of the nanocluster as well as the surface accessibility of small molecules for potential catalytic and biomedical applications.« less

Authors:

Chevrier, Daniel M.  ^[1];

• Search DOE PAGES for author "Chevrier, Daniel M."
• Search DOE PAGES for ORCID "0000-0002-0914-6714"

Conn, Brian E. ^[2]; Li, Bo  ^[3];

• Search DOE PAGES for author "Li, Bo"
• Search DOE PAGES for ORCID "0000-0002-2676-926X"

Jiang, De-en  ^[3];

• Search DOE PAGES for author "Jiang, De-en"
• Search DOE PAGES for ORCID "0000-0001-5167-0731"

Bigioni, Terry P.  ^[2];

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• Search DOE PAGES for ORCID "0000-0002-4931-1390"

Chatt, Amares  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-7725-6712"

Zhang, Peng  ^[1]

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• Search DOE PAGES for ORCID "0000-0003-3603-0175"

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+ Show Author Affiliations

1. Dalhousie Univ., Halifax, NS (Canada)
2. Univ. of Toledo, OH (United States)
3. Univ. of California, Riverside, CA (United States)

Publication Date:

Fri Jun 19 00:00:00 EDT 2020

Research Org.:

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:

National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

OSTI Identifier:

1712710

Grant/Contract Number:  

AC05-00OR22725; 0955148; 1905262; AC02-05CH11231; AC02-06CH11357

Resource Type:

Accepted Manuscript

Journal Name:

ACS Nano

Additional Journal Information:

Journal Volume: 14; Journal Issue: 7; Journal ID: ISSN 1936-0851

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; thiolate-silver nanocluster; coordinating solvents; cluster-solvent interactions; x-ray absorption spectroscopy; quantum