TY - JOUR
T1 - Interlocked catenane-like structure predicted in Au 24(SR) 20
T2 - Implication to structural evolution of thiolated gold clusters from homoleptic gold(I) thiolates to core-stacked nanoparticles
AU - Pei, Yong
AU - Pal, Rhitankar
AU - Liu, Chunyan
AU - Gao, Yi
AU - Zhang, Zhuhua
AU - Zeng, Xiao Cheng
N1 - Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].
PY - 2012/2/15
Y1 - 2012/2/15
N2 - Atomic structure of a recently synthesized ligand-covered cluster Au 24(SR) 20 [J. Phys. Chem. Lett., 2010, 1, 1003] is resolved based on the developed classical force-field based divide-and-protect approach. The computed UV-vis absorption spectrum and powder X-ray diffraction (XRD) curve for the lowest-energy isomer are in good agreement with experimental measurements. Unique catenane-like staple motifs are predicted for the first time in core-stacked thiolate-group (RS-) covered gold nanoparticles (RS-AuNPs), suggesting the onset of structural transformation in RS-AuNPs at relatively low Au/SR ratio. Since the lowest-energy structure of Au 24(SR) 20 entails interlocked Au 5(SR) 4 and Au 7(SR) 6 oligomers, it supports a recently proposed growth model of RS-AuNPs [J. Phys. Chem. Lett., 2011, 2, 990], that is, Au n(SR) n-1 oligomers are formed during the initial growth of RS-AuNPs. By comparing the Au-core structure of Au 24(SR) 20 with other structurally resolved RS-AuNPs, we conclude that the tetrahedral Au 4 motif is a prevalent structural unit for small-sized RS-AuNPs with relatively low Au/SR ratio. The structural prediction of Au 24(SR) 20 offers additional insights into the structural evolution of thiolated gold clusters from homoleptic gold(I) thiolate to core-stacked RS-AuNPs. Specifically, with the increase of interfacial bond length of Au(core)-S in RS-AuNPs, increasingly larger "metallic" Au-core is formed, which results in smaller HOMO-LUMO (or optical) gap. Calculations of electronic structures and UV-vis absorption spectra of Au 24(SR) 20 and larger RS-AuNPs (up to ∼2 nm in size) show that the ligand layer can strongly affect optical absorption behavior of RS-AuNPs. © 2012 American Chemical Society.
AB - Atomic structure of a recently synthesized ligand-covered cluster Au 24(SR) 20 [J. Phys. Chem. Lett., 2010, 1, 1003] is resolved based on the developed classical force-field based divide-and-protect approach. The computed UV-vis absorption spectrum and powder X-ray diffraction (XRD) curve for the lowest-energy isomer are in good agreement with experimental measurements. Unique catenane-like staple motifs are predicted for the first time in core-stacked thiolate-group (RS-) covered gold nanoparticles (RS-AuNPs), suggesting the onset of structural transformation in RS-AuNPs at relatively low Au/SR ratio. Since the lowest-energy structure of Au 24(SR) 20 entails interlocked Au 5(SR) 4 and Au 7(SR) 6 oligomers, it supports a recently proposed growth model of RS-AuNPs [J. Phys. Chem. Lett., 2011, 2, 990], that is, Au n(SR) n-1 oligomers are formed during the initial growth of RS-AuNPs. By comparing the Au-core structure of Au 24(SR) 20 with other structurally resolved RS-AuNPs, we conclude that the tetrahedral Au 4 motif is a prevalent structural unit for small-sized RS-AuNPs with relatively low Au/SR ratio. The structural prediction of Au 24(SR) 20 offers additional insights into the structural evolution of thiolated gold clusters from homoleptic gold(I) thiolate to core-stacked RS-AuNPs. Specifically, with the increase of interfacial bond length of Au(core)-S in RS-AuNPs, increasingly larger "metallic" Au-core is formed, which results in smaller HOMO-LUMO (or optical) gap. Calculations of electronic structures and UV-vis absorption spectra of Au 24(SR) 20 and larger RS-AuNPs (up to ∼2 nm in size) show that the ligand layer can strongly affect optical absorption behavior of RS-AuNPs. © 2012 American Chemical Society.
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U2 - 10.1021/ja208559y
DO - 10.1021/ja208559y
M3 - RGC 21 - Publication in refereed journal
SN - 0002-7863
VL - 134
SP - 3015
EP - 3024
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 6
ER -