A route to metalloligands consolidated silver nanoclusters by grafting thiacalix[4]arene onto polyoxovanadates.
basic_science · Level V
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- Record sourced from PubMed, PMID 37652941.
- Also identified by DOI 10.1038/s41467-023-41050-x and PMC identifier 10471715.
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Abstract
Metalloligands provide a potent strategy for manipulating the surface metal arrangements of metal nanoclusters, but their synthesis and subsequent installation onto metal nanoclusters remains a significant challenge. Herein, two atomically precise silver nanoclusters {Ag<sub>14</sub>[(TC4A)<sub>6</sub>(V<sub>9</sub>O<sub>16</sub>)](CyS)<sub>3</sub>} (Ag14) and {Ag<sub>43</sub>S[(TC4A)<sub>2</sub>(V<sub>4</sub>O<sub>9</sub>)]<sub>3</sub>(CyS)<sub>9</sub>(PhCOO)<sub>3</sub>Cl<sub>3</sub>(SO<sub>4</sub>)<sub>4</sub>(DMF)<sub>3</sub>·6DMF} (Ag43) are synthesized by controlling reaction temperature (H<sub>4</sub>TC4A = p-tert-butylthiacalix[4]arene). Interestingly, the 3D scaffold-like [(TC4A)<sub>6</sub>(V<sub>9</sub>O<sub>16</sub>)]<sup>11-</sup> metalloligand in Ag14 and 1D arcuate [(TC4A)<sub>2</sub>(V<sub>4</sub>O<sub>9</sub>)]<sup>6</sup><sup>-</sup> metalloligand in Ag43 exhibit a dual role that is the internal polyoxovanadates as anion template and the surface TC4A<sup>4-</sup> as the passivating agent. Furthermore, the thermal-induced structure transformation between Ag14 and Ag43 is achieved based on the temperature-dependent assembly process. Ag14 shows superior photothermal conversion performance than Ag43 in solid state indicating its potential for remote laser ignition. Here, we show the potential of two thiacalix[4]arene modified polyoxovanadates metalloligands in the assembly of metal nanoclusters and provide a cornerstone for the remote laser ignition applications of silver nanoclusters.