Chiral Ag<sub>23</sub> nanocluster with open shell electronic structure and helical face-centered cubic framework.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 29467372.
- Also identified by DOI 10.1038/s41467-018-03136-9 and PMC identifier 5821857.
- 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
We report the synthesis and crystal structure of a nanocluster composed of 23 silver atoms capped by 8 phosphine and 18 phenylethanethiolate ligands. X-ray crystallographic analysis reveals that the kernel of the Ag nanocluster adopts a helical face-centered cubic structure with C2 symmetry. The thiolate ligands show two binding patterns with the surface Ag atoms: tri- and tetra-podal types. The tetra-coordination mode of thiolate has not been found in previous Ag nanoclusters. No counter ion (e.g., Na+ and NO3-) is found in the single-crystal and the absence of such ions is also confirmed by X-ray photoelectron spectroscopy analysis, indicating electrical neutrality of the nanocluster. Interestingly, the nanocluster has an open shell electronic structure (i.e., 23(Ag 5s1)-18(SR) = 5e), as confirmed by electron paramagnetic resonance spectroscopy. Time-dependent density functional theory calculations are performed to correlate the structure and optical absorption/emission spectra of the Ag nanocluster.