Valence self-regulation of sulfur in nanoclusters.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 31803835.
- Also identified by DOI 10.1126/sciadv.aax7863 and PMC identifier 6874481.
- Licence recorded as CC BY-NC.
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Abstract
The valence self-regulation of sulfur from the "-2" valence state in thiols to the "-1" valence state in hydroxylated thiolates has been accomplished using the Pt<sub>1</sub>Ag<sub>28</sub> nanocluster as a platform-the first time that the "-1" valent sulfur has been detected as S<sup>-1</sup>. Two previously unknown nanoclusters, Pt<sub>1</sub>Ag<sub>28</sub>(SR)<sub>20</sub> and Pt<sub>1</sub>Ag<sub>28</sub>(SR)<sub>18</sub>(HO-SR)<sub>2</sub> (where SR represents 2-adamantanethiol), have been synthesized and characterized-in the latter nanocluster, the presence of hydroxyl induces the valence regulation of two special S atoms from "-2" (in SR) to "-1" valence state in the HO-S(Ag)R. Because of the contrasting nature of the capping ligands in these two nanoclusters [i.e., only SR in Pt<sub>1</sub>Ag<sub>28</sub>(SR)<sub>20</sub> or both SR- and HO-SR- in Pt<sub>1</sub>Ag<sub>28</sub>(SR)<sub>18</sub>(HO-SR)<sub>2</sub>], they exhibit differing shell architectures, even though their cores (Pt<sub>1</sub>Ag<sub>12</sub>) are in the same icosahedral configuration. Single-crystal x-ray diffraction analysis revealed their 1:1 cocrystallization, and mass spectrometry verified the presence of hydroxyls on Pt<sub>1</sub>Ag<sub>28</sub>(SR)<sub>18</sub>(HO-SR)<sub>2</sub>.