TY - JOUR
T1 - Isolation of the Au145(SR)60X compound (R =: N -butyl, n -pentyl; X = Br, Cl)
T2 - Novel gold nanoclusters that exhibit properties subtly distinct from the ubiquitous icosahedral Au144(SR)60compound
AU - Dainese, Tiziano
AU - Antonello, Sabrina
AU - Bonacchi, Sara
AU - Morales-Martinez, Daniel
AU - Venzo, Alfonso
AU - Black, David M.
AU - Mozammel Hoque, M.
AU - Whetten, Robert L.
AU - Maran, Flavio
N1 - Publisher Copyright:
© The Royal Society of Chemistry.
PY - 2021/9/28
Y1 - 2021/9/28
N2 - We report the identification and quantitative isolation of Au145(SR)60X (R = n-butyl, n-pentyl; X = halide) along with elucidation of key properties as compared to the corresponding ubiquitous chiral-icosahedral Au144(SR)60 cluster known to have a central vacancy. The stoichiometries were assessed by electrospray mass spectrometry (ESI-MS) at isotopic resolution, and induced dissociation patterns indicate the 'extra' (Au,Br) atoms are strongly bound components of these structures. Voltammetric and spectroscopic characterization reveals Au145(SR)60X behaviors that are qualitatively similar to yet fascinatingly distinct from those of Au144(SR)60. (1H,13C)-NMR spectra clearly show how both Au145(SR)60X and Au144(SR)60 are capped by 12 distinct ligand types of 5-fold equivalence, as was recently established for Au144(SR)60 capped by shorter ligands, demonstrating that this novel cluster shares the same chiral-icosahedral motif. Intriguingly, Au145(SR)60X is strongly near-IR luminescent, whereas under comparable conditions Au144(SR)60 barely emits. The photoluminescence pattern of Au145(SR)60X is very similar to that observed for Au25(SR)18, which contains the Au13 core. The combined results are interpreted as consistent with neutral Au145(SR)60X as a diamagnetic species, electronically and structurally similar to the corresponding Au144(SR)60 compounds.
AB - We report the identification and quantitative isolation of Au145(SR)60X (R = n-butyl, n-pentyl; X = halide) along with elucidation of key properties as compared to the corresponding ubiquitous chiral-icosahedral Au144(SR)60 cluster known to have a central vacancy. The stoichiometries were assessed by electrospray mass spectrometry (ESI-MS) at isotopic resolution, and induced dissociation patterns indicate the 'extra' (Au,Br) atoms are strongly bound components of these structures. Voltammetric and spectroscopic characterization reveals Au145(SR)60X behaviors that are qualitatively similar to yet fascinatingly distinct from those of Au144(SR)60. (1H,13C)-NMR spectra clearly show how both Au145(SR)60X and Au144(SR)60 are capped by 12 distinct ligand types of 5-fold equivalence, as was recently established for Au144(SR)60 capped by shorter ligands, demonstrating that this novel cluster shares the same chiral-icosahedral motif. Intriguingly, Au145(SR)60X is strongly near-IR luminescent, whereas under comparable conditions Au144(SR)60 barely emits. The photoluminescence pattern of Au145(SR)60X is very similar to that observed for Au25(SR)18, which contains the Au13 core. The combined results are interpreted as consistent with neutral Au145(SR)60X as a diamagnetic species, electronically and structurally similar to the corresponding Au144(SR)60 compounds.
UR - http://www.scopus.com/inward/record.url?scp=85116011926&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85116011926&partnerID=8YFLogxK
U2 - 10.1039/d1nr04745k
DO - 10.1039/d1nr04745k
M3 - Article
C2 - 34499056
AN - SCOPUS:85116011926
SN - 2040-3364
VL - 13
SP - 15394
EP - 15402
JO - Nanoscale
JF - Nanoscale
IS - 36
ER -