手性金团簇的动力学控制合成、表征及性质研究

项目名称： 手性金团簇的动力学控制合成、表征及性质研究

项目编号： No.20871112

项目类型： 面上项目

立项/批准年度： 2009

项目学科： 金属学与金属工艺

项目作者： 朱满洲

作者单位： 安徽大学

项目金额： 33万元

中文摘要： 合成一系列手性取代苯乙硫醇衍生物作为配体。通过动力学控制Au(I):SR中间体的形成，合成纳米金团簇Aun(SR)m(n为金原子个数，m为配体个数)。综合应用正相柱层析、反相柱层析、排阻色谱、逆流层析、制备HPLC等现代分离方法纯化金团簇;STM、TEM观察金团簇的大小，计算金团簇中金原子个数；TGA研究金团簇中金与有机物比；结合UV-vis、HNMR、IR、MS、单晶X射线衍射、元素分析、电化学分析等现代分析手段鉴定所合成的纳米金团簇的组成、结构及理化性质。应用旋光光谱、圆二色谱研究手性金团簇的光学性质;穆斯堡尔光谱与扫描隧道显微镜观察所合成的手性金团簇的结构;通过对手性金团簇进行单晶培养，应用单晶X射线衍射研究手性金团簇的晶体结构，从而弄清手性金团簇手性的本质。

中文关键词： 手性；金；纳米团簇；控制合成；表征

英文摘要： A series of chiral thiols (R- and S-isomers) and chiral gold nanoparticles,for example: Au25 nanosphere, Au25 nanorod and Au38, chirally modified phenylethylthiolate ( _SCH2C*H-(CH3)Ph) at the 2-position as ligand, were designed and synthesized. These optically active Au25 nanospheres are close analogues of the optically nonactive phenylethylthioalte capped Au25 nanoparticles, and the latter's crystal structure is known. On the basis of the atomic and electronic structures of these well-defined Au25 nanoparticles, we have explicitly revealed that the ligands and surface gold atoms of Au25 play a critical role in effecting the circular dichroism responses from the nanoparticles. Similar effects are also observed in chiral Au25 nanorods. The mixing of electronic states of ligands with those of surface gold atoms constitutes the fundamental origin of chirality in such nanoparticles. Two new gold thiolate clusters with molecular purity Au24(SC2H4Ph)20 and Au20(SC2H4Ph)16 were synthesized and characterized in this work. These two nanoclusters show obviously quantum confinement of electrons in the particle.

英文关键词： Chirality;gold;nanocluster;controlled synthesis;characterization