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Title: Au 38 (SPh) 24 : Au 38 Protected with Aromatic Thiolate Ligands

Abstract

Au38(SR)24 is one of the most extensively investigated gold nanomolecules along with Au25(SR)18 and Au144(SR)60. However, so far it has only been prepared using aliphatic-like ligands, where R = –SC6H13, -SC12H25 and –SCH2CH2Ph. Au38(SCH2CH2Ph)24 when reacted with HSPh undergoes core-size conversion to Au36(SPh)24, and existing literature suggest that Au38(SPh)24 cannot be synthesized. Here, contrary to prevailing knowledge, we demonstrate that Au38(SPh)24 can be prepared if the ligand exchanged conditions are optimized, without any formation of Au36(SPh)24. Conclusive evidence is presented in the form of MALDI-MS, ESI-MS characterization, and optical spectra of Au38(SPh)24 in a solid glass form showing distinct differences from that of Au38(S-aliphatic)24. Theoretical analysis confirms experimental assignment of the optical spectrum and shows that the stability of Au38(SPh)24 is comparable to that of its aliphatic analogues, but results from different physical origins, with a significant component of ligand-ligand attractive interactions.

Authors:
; ; ; ; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1353331
Report Number(s):
PNNL-SA-122665
Journal ID: ISSN 1948-7185; 49645; KP1704020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry Letters; Journal Volume: 8; Journal Issue: 7
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Rambukwella, Milan, Burrage, Shayna, Neubrander, Marie, Baseggio, Oscar, Aprà, Edoardo, Stener, Mauro, Fortunelli, Alessandro, and Dass, Amala. Au 38 (SPh) 24 : Au 38 Protected with Aromatic Thiolate Ligands. United States: N. p., 2017. Web. doi:10.1021/acs.jpclett.7b00193.
Rambukwella, Milan, Burrage, Shayna, Neubrander, Marie, Baseggio, Oscar, Aprà, Edoardo, Stener, Mauro, Fortunelli, Alessandro, & Dass, Amala. Au 38 (SPh) 24 : Au 38 Protected with Aromatic Thiolate Ligands. United States. doi:10.1021/acs.jpclett.7b00193.
Rambukwella, Milan, Burrage, Shayna, Neubrander, Marie, Baseggio, Oscar, Aprà, Edoardo, Stener, Mauro, Fortunelli, Alessandro, and Dass, Amala. Tue . "Au 38 (SPh) 24 : Au 38 Protected with Aromatic Thiolate Ligands". United States. doi:10.1021/acs.jpclett.7b00193.
@article{osti_1353331,
title = {Au 38 (SPh) 24 : Au 38 Protected with Aromatic Thiolate Ligands},
author = {Rambukwella, Milan and Burrage, Shayna and Neubrander, Marie and Baseggio, Oscar and Aprà, Edoardo and Stener, Mauro and Fortunelli, Alessandro and Dass, Amala},
abstractNote = {Au38(SR)24 is one of the most extensively investigated gold nanomolecules along with Au25(SR)18 and Au144(SR)60. However, so far it has only been prepared using aliphatic-like ligands, where R = –SC6H13, -SC12H25 and –SCH2CH2Ph. Au38(SCH2CH2Ph)24 when reacted with HSPh undergoes core-size conversion to Au36(SPh)24, and existing literature suggest that Au38(SPh)24 cannot be synthesized. Here, contrary to prevailing knowledge, we demonstrate that Au38(SPh)24 can be prepared if the ligand exchanged conditions are optimized, without any formation of Au36(SPh)24. Conclusive evidence is presented in the form of MALDI-MS, ESI-MS characterization, and optical spectra of Au38(SPh)24 in a solid glass form showing distinct differences from that of Au38(S-aliphatic)24. Theoretical analysis confirms experimental assignment of the optical spectrum and shows that the stability of Au38(SPh)24 is comparable to that of its aliphatic analogues, but results from different physical origins, with a significant component of ligand-ligand attractive interactions.},
doi = {10.1021/acs.jpclett.7b00193},
journal = {Journal of Physical Chemistry Letters},
number = 7,
volume = 8,
place = {United States},
year = {Tue Mar 21 00:00:00 EDT 2017},
month = {Tue Mar 21 00:00:00 EDT 2017}
}