Robust, Highly Luminescent Au13 Superatoms Protected by N-Heterocyclic Carbenes
Abstract
Gold superatom nanoclusters stabilized entirely by N-heterocyclic carbenes (NHCs) are reported. The reduction of well-defined NHC–Au–Cl complexes produces clusters com-prised of an icosahedral Au13 core surrounded by a symmetrical arrangement of 9 NHCs and 3 chlorides. X-ray crystallography shows that the clusters are characterized by multiple CH–π and π–π interactions, which rigidify the ligand and likely con-tribute to the exceptionally high photoluminescent quantum yields observed, up to 16.0 %, which is significantly greater than the most luminescent ligand-protected Au13 superatom cluster. Density functional theory analysis suggests that clus-ters are 8-electron superatoms with a wide HOMO-LUMO energy gap of 2 eV. Consistent with this, the clusters have high stability relative to all-phosphine clusters.
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Format
Articles
Research article
Published
2019
Series
Subjects
Publication in research information system
Publisher
American Chemical Society
The permanent address of the publication
https://urn.fi/URN:NBN:fi:jyu-201909174173Use this for linking
Review status
Peer reviewed
ISSN
0002-7863
DOI
https://doi.org/10.1021/jacs.9b07854
Language
English
Published in
Journal of the American Chemical Society
Citation
- Narouz, M. R., Takano, S., Lummis, P. A., Levchenko, T. I., Nazemi, A., Kaappa, S., Malola, S., Yousefalizadeh, G., Calhoun, L. A., Stamplecoskie, K. G., Häkkinen, H., Tsukuda, T., & Crudden, C. M. (2019). Robust, Highly Luminescent Au13 Superatoms Protected by N-Heterocyclic Carbenes. Journal of the American Chemical Society, 141(38), 14997-15002. https://doi.org/10.1021/jacs.9b07854
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Additional information about funding
The Natural Sciences and Engineering Research Council of Canada (NSERC) and the Canada Foundation for Innovation (CFI) are thanked for financial support of this work in terms of operating and equipment grants to CMC and KS. MN thanks the Ontario government for an OGS fellowship and Mitacs–JSPS for funding to travel to Japan. HH thanks the Academy of Finland for support for Academy Professorship and CSC – the Finnish IT Center for Science for generous computers resources. SK thanks the Väisälä Foundation for a personal PhD study grant. TT acknowledges financial support from the Elements Strategy Initiative for Catalysts & Batteries (ESICB) and the Nanotechnology Platform (Project No. 12024046) from the Ministry of Education, Culture, Sports, Science, and Technology (MEXT) of Japan and a Grant-in-Aid for Scientific Research (A) (Grant No. 17H01182) from the Japan Society for the Promotion of Science (JSPS). Dr. Renee Man is thanked for the preparation of the TOC graphic.
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