A1 Journal article (refereed)
Ag44(EBT)26(TPP)4 Nanoclusters with Tailored Molecular and Electronic Structure (2021)
Hyeon, T., Bootharaju, M. S., Lee, S., Deng, G., Malola, S., Baek, W., Häkkinen, H., & Zheng, N. (2021). Ag44(EBT)26(TPP)4 Nanoclusters with Tailored Molecular and Electronic Structure. Angewandte Chemie, 60(16), 9038-9044. https://doi.org/10.1002/anie.202015907
JYU authors or editors
Publication details
All authors or editors: Hyeon, Taeghwan; Bootharaju, Megalamane S.; Lee, Sanghwa; Deng, Guocheng; Malola, Sami; Baek, Woonhyuk; Häkkinen, Hannu; Zheng, Nanfeng
Journal or series: Angewandte Chemie
ISSN: 1433-7851
eISSN: 1521-3773
Publication year: 2021
Publication date: 28/12/2020
Volume: 60
Issue number: 16
Pages range: 9038-9044
Publisher: Wiley-VCH Verlag
Publication country: Germany
Publication language: English
DOI: https://doi.org/10.1002/anie.202015907
Publication open access: Not open
Publication channel open access:
Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/73918
Abstract
Although atomically precise metalloid nanoclusters (NCs) of identical size with distinctly different molecular structures are highly desirable to understand the structural effects on the intriguing optical and photophysical properties, their synthesis remains highly challenging. Herein, we employed phosphine and thiol capping ligands featuring appropriate steric effects and synthesized a charge‐neutral Ag NC with the formula, Ag 44 (EBT) 26 (TPP) 4 (EBT: 2‐ethylbenzenethiolate; TPP: triphenylphosphine). The single‐crystal X‐ray structure reveals that this NC has a hollow metal core of Ag 12 @Ag 20 and a metal‐ligand shell of Ag 12 (EBT) 26 (TPP) 4 . The presence of mixed ligands and long V‐shaped metal‐ligand motifs on this NC has resulted in the enhancement of NIR‐II photoluminescence quantum yield by >25‐folds compared to an all‐thiolate‐stabilized anionic [Ag 44 (SR) 30 ] 4― NC (SR: thiolate). Time‐dependent density functional calculations show that our Ag 44 NC is an 18‐electron superatom with a modulated electronic structure as compared to the [Ag 44 (SR) 30 ] 4― anion, significantly influencing its optical properties.
Keywords: nanoparticles; clusters; silver
Free keywords: silver; nanoclusters; single crystal X-ray structure; NIR-II photoluminescence; superatom
Contributing organizations
Related projects
- Metalli-molekyyli-rajapintojen nanorakenteet (NaMeMolnt)
- Häkkinen, Hannu
- Research Council of Finland
- Metalli-molekyyli-rajapintojen nanorakenteet (NaMeMoInt)
- Häkkinen, Hannu
- Research Council of Finland
- NANOSTRUCTURED METAL – MOLECULE INTERFACES
- Häkkinen, Hannu
- Research Council of Finland
Ministry reporting: Yes
Reporting Year: 2021
JUFO rating: 3