Deciphering synergetic core-shell transformation from [Mo<sub>6</sub>O<sub>22</sub>@Ag<sub>44</sub>] to [Mo<sub>8</sub>O<sub>28</sub>@Ag<sub>50</sub>].
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 30353007.
- Also identified by DOI 10.1038/s41467-018-06755-4 and PMC identifier 6199286.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
The structural transformation of high-nuclearity silver clusters from one to another induced by specific stimuli is of scientific significance in terms of both cluster synthesis and reactivity. Herein, we report two silver-thiolate clusters, [Mo<sub>6</sub>O<sub>22</sub>@Ag<sub>44</sub>] and [Mo<sub>8</sub>O<sub>28</sub>@Ag<sub>50</sub>], which are templated by isopolymolybdates inside and covered by <sup>i</sup>PrS<sup>-</sup> and PhCOO<sup>-</sup> ligands on the surfaces. Amazingly, the [Mo<sub>8</sub>O<sub>28</sub>@Ag<sub>50</sub>] can be transformed from [Mo<sub>6</sub>O<sub>22</sub>@Ag<sub>44</sub>] by adding PhCOOH which increases the degree of condensation of molybdates template from Mo<sub>6</sub>O<sub>22</sub><sup>8-</sup> to Mo<sub>8</sub>O<sub>28</sub><sup>8-</sup>, then enlarging the outer silver shell from Ag<sub>44</sub> to Ag<sub>50</sub>. The evolution of solution species revealed by time-dependent electrospray ionization mass spectrometry (ESI-MS) suggests a breakage-growth-reassembly (BGR) transformation mechanism. These results not only provide a combined assembly strategy (anion-template + induced transformation) for the synthesis of silver-thiolate clusters but also help us to better understand the complex transformation process underpinning the assembly system.