RIKEN Advanced Science Institute, Wako, Saitama 351-0198, Japan.
Nanoscale. 2012 Jul 21;4(14):4206-10. doi: 10.1039/c2nr30501a. Epub 2012 May 21.
We have studied the electrochemical and thermodynamic stability of Au(25)(SR)(18)(-), Au(38)(SR)(24), and Au(102)(SR)(44), R = CH(3), C(6)H(13), CH(2)CH(2)Ph, Ph, PhF, and PhCOOH, in order to examine ligand effects on the stability of thiol-stabilized gold nanoclusters, Au(m)(SR)(n). Aliphatic thiols, in general, have higher electrochemical and thermodynamic stability than aromatic thiols, and the -SCH(2)CH(2)Ph thiol is particularly appealing because of its high electrochemical and thermodynamic stability. The stabilization of Au(m) by nSR for Au(m)(SR)(n) can be rationalized by the stabilization of an Au atom by an SR for the simple molecule AuSR, regardless of interligand interaction and system size and shape. Thiol moieties play a strong role in the electron oxidation and reduction of Au(m)(SR)(n). Accounting for the characteristics of thiol ligands is essential for understanding the electronic and thermodynamic stability of thiol-stabilized gold nanoclusters.
我们研究了 Au(25)(SR)(18)(-)、Au(38)(SR)(24)和 Au(102)(SR)(44)（其中 R = CH(3)、C(6)H(13)、CH(2)CH(2)Ph、Ph、PhF 和 PhCOOH）的电化学和热力学稳定性，以考察配体对巯基稳定的金纳米簇 Au(m)(SR)(n)稳定性的影响。一般来说，脂肪族硫醇比芳香族硫醇具有更高的电化学和热力学稳定性，而 -SCH(2)CH(2)Ph 硫醇因其高电化学和热力学稳定性而特别吸引人。对于简单分子 AuSR，Au(m)被 nSR 稳定，可以通过 Au 原子被 SR 稳定来合理化，而不管配体间相互作用以及系统的大小和形状。硫醇部分在 Au(m)(SR)(n)的电子氧化还原中起着重要作用。考虑到硫醇配体的特点，对于理解巯基稳定的金纳米簇的电子和热力学稳定性至关重要。
