Silver monolayer-protected clusters (MPCs), also known as molecular nanoparticles, have significant potential for next generation technological applications (nano-carrier for drug delivery, bio-imaging, photovoltaics, etc.). The syntheses of this class of nanoparticles are not yet well understood, however, so designing syntheses to produce specific technologically important MPC products remains a challenge. Syntheses can be designed and controlled more easily if the synthetic mechanism is known. Two different synthetic mechanisms have been proposed, namely the “size focusing” and “condensation” models, but we have observed that silver-glutathione (Ag:SG) MPC formation is not compatible with these models. Rather, the mechanism for Ag:SG MPC formation progressed through the growth of smaller sizes into larger sizes of previously known species. Here, we describe a new “sequential growth” model of MPC synthesis wherein their formation involves the growth of smaller species into larger species, sequentially, from one known size to another. This sequential growth pathway progresses through a potential energy landscape that is defined by thermodynamic preferences for stable sizes (controlled by choices of metals, ligands, solvents, etc.) and their associated kinetic barriers to the transformation of one size into another. It was also found that oxidation reactions played an important role in the synthesis of Ag:SG MPCs, which will also be discussed. Together, this work begins to better define the mechanisms of silver MPC synthesis.

Understanding the synthesis mechanism of silver-glutathione monolayer-protected clusters

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.