TY - JOUR
T1 - The smallest thiolated gold superatom complexes
AU - Jiang, De En
AU - Whetten, Robert L.
AU - Luo, Weidong
AU - Dai, Sheng
PY - 2009
Y1 - 2009
N2 - The superatom concept of metallic cluster valence is based on the electron-shell model as first proposed to explain the special stability of certain metal-atom clusters generated in the gas phase. It accounts for the magic-number series 2, 8, 18, 34, 58,. by shell-closing of the superatom orbitals 1S, 1P, 1D,. Recently, the superatom-complex concept has been introduced to explain the compositions of high-yield gold-cluster compounds, especially Au 25(SR) 18 - and Au 102(SR) 44 (with -SR being a thiolate group), corresponding to the magic numbers of 8 and 58, respectively. Surprisingly, no thiolated gold cluster accounting for the first closing (electron count 2) has yet been determined. Structure-bonding considerations lead us to propose Au 12(SR) 9+ as the superior candidate for the smallest thiolated gold superatom. This cluster features an octahedron core covered by three RS(AuSR) 2 motifs. It has a unique C 3 axis, is chiral, and possesses ideal aurophilic interactions and, therefore, should exist in nature. The folding of thiol-rich biomolecules may help us to realize this complex, which may also be prepared from available phosphine-ligated gold clusters.
AB - The superatom concept of metallic cluster valence is based on the electron-shell model as first proposed to explain the special stability of certain metal-atom clusters generated in the gas phase. It accounts for the magic-number series 2, 8, 18, 34, 58,. by shell-closing of the superatom orbitals 1S, 1P, 1D,. Recently, the superatom-complex concept has been introduced to explain the compositions of high-yield gold-cluster compounds, especially Au 25(SR) 18 - and Au 102(SR) 44 (with -SR being a thiolate group), corresponding to the magic numbers of 8 and 58, respectively. Surprisingly, no thiolated gold cluster accounting for the first closing (electron count 2) has yet been determined. Structure-bonding considerations lead us to propose Au 12(SR) 9+ as the superior candidate for the smallest thiolated gold superatom. This cluster features an octahedron core covered by three RS(AuSR) 2 motifs. It has a unique C 3 axis, is chiral, and possesses ideal aurophilic interactions and, therefore, should exist in nature. The folding of thiol-rich biomolecules may help us to realize this complex, which may also be prepared from available phosphine-ligated gold clusters.
UR - http://www.scopus.com/inward/record.url?scp=70350020483&partnerID=8YFLogxK
U2 - 10.1021/jp9035937
DO - 10.1021/jp9035937
M3 - Article
AN - SCOPUS:70350020483
SN - 1932-7447
VL - 113
SP - 17291
EP - 17295
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 40
ER -