Department of Chemistry and Biochemistry, University of Mississippi , Oxford, Mississippi 38677, United States.
Langmuir. 2017 Oct 17;33(41):10958-10964. doi: 10.1021/acs.langmuir.7b03080. Epub 2017 Oct 3.
Phenylethanethiol protected nanomolecules such as Au, Au, and Au are widely studied by a broad range of scientists in the community, owing primarily to the availability of simple synthetic protocols. However, synthetic methods are not available for other ligands, such as aromatic thiol and bulky ligands, impeding progress. Here we report the facile synthesis of three distinct nanomolecules, Au(SCHCHPh), Au(SPh-tBu), and Au(S-tBu), exclusively, starting from a common Au(glutathione) (where n and m are number of gold atoms and glutathiolate ligands) starting material upon reaction with HSCHCHPh, HSPh-tBu, and HStBu, respectively. The systematic synthetic approach involves two steps: (i) synthesis of kinetically controlled Au(glutathione) crude nanocluster mixture with 1:4 gold to thiol molar ratio and (ii) thermochemical treatment of the purified nanocluster mixture with excess thiols to obtain thermodynamically stable nanomolecules. Thermochemical reactions with physicochemically different ligands formed highly monodispersed, exclusively three different core-size nanomolecules, suggesting a ligand induced core-size conversion and structural transformation. The purpose of this work is to make available a facile and simple synthetic method for the preparation of Au(SCHCHPh), Au(SPh-tBu), and Au(S-tBu), to nonspecialists and the broader scientific community. The central idea of simple synthetic method was demonstrated with other ligand systems such as cyclopentanethiol (HSCH), cyclohexanethiol(HSCH), para-methylbenzenethiol(pMBT), 1-pentanethiol(HSCH), 1-hexanethiol(HSCH), where Au(SCH), Au(SCH), Au(pMBT), Au(SCH), and Au(SCH) were obtained, respectively.
苯乙硫醇保护的纳米分子,如 Au、Au 和 Au,由于其简单的合成方案,被广大科学界的广泛研究。然而,对于其他配体,如芳香硫醇和大体积配体,合成方法并不适用,这阻碍了研究的进展。在这里,我们报道了一种简便的合成方法,可以从常见的 Au(谷胱甘肽)(其中 n 和 m 是金原子和谷胱甘肽配体的数量)起始原料出发,分别与 HSCHCHPh、HSPh-tBu 和 HStBu 反应,仅得到三种不同的纳米分子,即 Au(SCHCHPh)、Au(SPh-tBu) 和 Au(S-tBu)。系统的合成方法包括两步:(i)合成动力学控制的 Au(谷胱甘肽)粗纳米团簇混合物,金与硫醇的摩尔比为 1:4;(ii)用过量的硫醇对纯化的纳米团簇混合物进行热化学处理,以得到热力学稳定的纳米分子。与物理化学性质不同的配体进行热化学反应,形成了高度单分散的、仅三种不同核心尺寸的纳米分子,这表明配体诱导了核心尺寸的转换和结构的转变。这项工作的目的是为非专业人士和更广泛的科学界提供一种简便的合成方法,用于制备 Au(SCHCHPh)、Au(SPh-tBu) 和 Au(S-tBu)。简单合成方法的核心思想还通过其他配体系统如环戊硫醇(HSCH)、环己硫醇(HSCH)、对甲基苯硫醇(pMBT)、1-戊硫醇(HSCH)和 1-己硫醇(HSCH)得到了验证,分别得到了 Au(SCH)、Au(SCH)、Au(pMBT)、Au(SCH)和 Au(SCH)。