Electronic Structures and Photoluminescence of Monolayer-Protected Metal Clusters

单层保护金属团簇的电子结构和光致发光

• 批准号: 16510079
• 负责人: TSUKUDA Tatsuya
• 金额: $ 1.86万
• 依托单位: Institute for Molecular Science
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16510079/
• 关键词: gold cluster; thiol; PAGE; mass analysis; photoluminescence; GPC; グルタチオン; エレクトロスプレーイオン化質量分析; バンド内吸収

We have developed a synthetic method of thiolate-protected gold clusters with well-defined chemical compositions. The method is based on size separation by using polyacrylamide gel electrophoresis (PAGE) and gel permeation chromatography (GPC) and mass spectrometric characterization. Electronic and geometrical structures of the thiolated gold (Au : SR) clusters thus synthesized were studied by using various spectroscopic methods and theoretical calculations. The findings are summarized as follows.1)The Au : SR clusters formed by reduction of the corresponding Au(I)-SR polymer correspond to trapped intermediates of the growing clusters. We observed several magic-numbered gold clusters such as Au25(SG)18 and Au55(SC18)32, where GSH and C18SH represent glutathione and octadecanethiol, respectively.2)The small Au : SR clusters exhibit photoluminescence with quantum yield of 10^<-3>- 10^<-4>, which is significantly larger than that of bulk gold (10^<-10>). This enhancement is attributable to the quasi-molecular electronic structures. The emission wavelengths are nearly constant irrespective of the core size. This suggests that the PL originates from the Au-SR ring structures attached on the gold cluster surface. This structure model is supported by theoretical studies.

我们开发了一种具有明确化学成分的硫醇保护金簇的合成方法。该方法基于使用聚丙烯酰胺凝胶电泳 (PAGE) 和凝胶渗透色谱 (GPC) 进行尺寸分离以及质谱表征。通过使用各种光谱方法和理论计算，研究了由此合成的硫醇化金（Au：SR）团簇的电子和几何结构。研究结果概括如下：1)通过还原相应的Au(I)-SR聚合物形成的Au:SR簇对应于生长簇中被捕获的中间体。我们观察到了几个幻数金簇，例如Au25(SG)18和Au55(SC18)32，其中GSH和C18SH分别代表谷胱甘肽和十八烷硫醇。2)小Au : SR簇表现出光致发光，量子产率为10^<-3>- 10^<-4>，明显大于块状金。 (10^<-10>)。这种增强归因于准分子电子结构。无论纤芯尺寸如何，发射波长几乎恒定。这表明 PL 源自金簇表面附着的 Au-SR 环结构。该结构模型得到了理论研究的支持。

项目成果

Spectroscopic investigation of dendrimer-encapsulated gold nanoclusters

树枝状聚合物封装的金纳米团簇的光谱研究

• 期刊: Trans.MRS-J. (in press)
• 作者: M.Imamura;T.Miyashita;A.Tanaka;H.Yasuda;Y.Yanagimoto;Y.Negishi;T.Tsukuda
• 通讯作者: T.Tsukuda

Chromatographic isolation of "missing" Au55 clusters protected by alkanethiolates

• DOI: 10.1021/ja061659t
• 发表时间: 2006-05-10
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Tsunoyama, Hironori;Negishi, Yuichi;Tsukuda, Tatsuya
• 通讯作者: Tsukuda, Tatsuya

Colloidal gold nanoparticles as catalyst for carbon-carbon bond formation: Application to aerobic homocoupling of phenylboronic acid in water

• DOI: 10.1021/la0478189
• 发表时间: 2004-12-21
• 期刊: LANGMUIR
• 影响因子: 3.9
• 作者: Tsunoyama, H;Sakurai, H;Tsukuda, T
• 通讯作者: Tsukuda, T

Large-scale synthesis of thiolated Au_25 Clusters via ligand exchange reactions phosophine-stabilized Au_11 clusters

通过配体交换反应大规模合成硫醇化 Au_25 簇 磷酸稳定的 Au_11 簇

• 发表时间: 2005
• 期刊: Journal of the American Chemical Society 127
• 作者: Y.Shichibu;Y.Negishi;T.Tukuda;T.Teranishi
• 通讯作者: T.Teranishi

Subnanometer-sized gold clusters with dual molecular receptors synthesis and assembly one-dimensional arrangements

具有双分子受体合成和组装一维排列的亚纳米级金簇

• 发表时间: 2005
• 期刊: Chemistry Letters 34
• 作者: Y.Negishi;H.Tsunoyama;Y.Yanagimoto;T.Tsukuda
• 通讯作者: T.Tsukuda