A Dynamic Silver(I) Nanocluster Holds Together a 3 × 3 Self-Assembled Grid
Metal ions with well-defined coordination geometries can serve as fixed joints within self-assembled architectures, defining the relative orientations of ligands within higher-order superstructures. The exchange of ligands and metal ions between different positions is slow, involving disruption or distortion. Here we report a series of Ag<sup>I</sup><sub>12</sub>X<sub>4</sub>L<sub>6</sub> 3 × 3 metal-organic grid-like structures, where the core Ag<sup>I</sup><sub>12</sub>X<sub>4</sub> nanocluster is in dynamic motion, with Ag<sup>I</sup> ions moving between different binding sites, with concomitant conformational changes of the organic ligands, which continue to occupy well-defined positions nevertheless. The identity of the incorporated halide anion governs the activation barrier for silver ion exchange, thus enabling rate control in response to two distinct stimuli: by changing the temperature, and by exchanging one halide for another. The dynamic nanocluster within these grids thus provides a new mode of using metal ions in coordination-driven self-assembly, establishing that the mobile Ag<sup>I</sup> ions behave in similar ways to Ag<sup>0</sup> atoms in surface-bound clusters and in silver nanoparticles. The kinetic parameters determined in this work, and the techniques developed to measure them, could serve the scientific community to provide additional insight into dynamic metal nanoclusters.
Authors
- Tanya K. Ronson (ORCID: https://orcid.org/0000-0002-6917-3685)
- Silvia Marchesan (ORCID: https://orcid.org/0000-0001-6089-3873)
- Andrew W. Heard (ORCID: https://orcid.org/0000-0002-6815-4618)
- Jonathan R. Nitschke (ORCID: https://orcid.org/0000-0002-4060-5122)
- Peter Gierth
- Martin Welch (ORCID: https://orcid.org/0000-0003-3646-1733)
- Giovanni Maria Pavan (ORCID: https://orcid.org/0000-0002-3473-8471)
- Tomáš Deingruber (ORCID: https://orcid.org/0000-0002-6017-9490)
- Simone Adorinni (ORCID: https://orcid.org/0000-0002-6888-7635)
- John D. Thoburn (ORCID: https://orcid.org/0000-0002-2422-8478)
- David R. Spring (ORCID: https://orcid.org/0000-0001-7355-2824)
- Barbara Rossi (ORCID: https://orcid.org/0000-0003-1357-8074)
- Luca Pesce (ORCID: https://orcid.org/0000-0001-6364-9577)
Institutions
- Centre National de la Recherche Scientifique (FR)
- University of Trieste (IT)
- University of Applied Sciences and Arts of Southern Switzerland (CH)
- Politecnico di Torino (IT)
- Randolph–Macon College (US)
- University of Cambridge (GB)
- Elettra-Sincrotrone Trieste S.C.p.A. (IT)
- International School of Trieste (IT)
- Pharmaceutical Formulations (United States) (US)
- Chimie et Interdisciplinarité, Synthèse, Analyse, Modélisation (FR)
- Chemical Pharmaceutical Research Institute (BG)
- University of Birmingham (GB)
- Ashland (United States) (US)
- Nantes Université (FR)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-08-18
- DOI
- https://doi.org/10.1021/jacs.5c07271
- Citations
- 2
- Primary Topic
- Nanocluster Synthesis and Applications
- Type
- article
- Field-Weighted Citation Impact
- 1.04
Funders
- Astex Pharmaceuticals
- Leverhulme Trust
- Cystic Fibrosis Trust
- Agence Nationale de la Recherche
- Defense Advanced Research Projects Agency
- Medical Research Council
- Engineering and Physical Sciences Research Council
- H2020 European Research Council