Department of Chemical and Biomolecular Engineering, National University of Singapore, 10 Kent Ridge Crescent, Singapore 119260.
J Am Chem Soc. 2012 Oct 10;134(40):16662-70. doi: 10.1021/ja306199p. Epub 2012 Oct 1.
A fundamental understanding of the luminescence of Au-thiolate nanoclusters (NCs), such as the origin of emission and the size effect in luminescence, is pivotal to the development of efficient synthesis routes for highly luminescent Au NCs. This paper reports an interesting finding of Au(I)-thiolate complexes: strong luminescence emission by the mechanism of aggregation-induced emission (AIE). The AIE property of the complexes was then used to develop a simple one-pot synthesis of highly luminescent Au-thiolate NCs with a quantum yield of ~15%. Our key strategy was to induce the controlled aggregation of Au(I)-thiolate complexes on in situ generated Au(0) cores to form Au(0)@Au(I)-thiolate core-shell NCs where strong luminescence was generated by the AIE of Au(I)-thiolate complexes on the NC surface. We were able to extend the synthetic strategy to other thiolate ligands with added functionalities (in the form of custom-designed peptides). The discovery (e.g., identifying the source of emission and the size effect in luminescence) and the synthesis protocols in this study can contribute significantly to better understanding of these new luminescence probes and the development of new synthetic routes.
对金-硫醇纳米团簇（NCs）的发光机制（如发光的起源和尺寸效应）有基本的了解，对于开发高效合成高发光金 NCs 的方法至关重要。本文报道了金（I）-硫醇配合物的一个有趣发现：通过聚集诱导发光（AIE）机制产生强发光发射。然后，利用该配合物的 AIE 性质，开发了一种简单的一锅法合成具有~15%量子产率的高发光金-硫醇 NCs 的方法。我们的关键策略是在原位生成的 Au(0)核上诱导 Au(I)-硫醇配合物的受控聚集，形成 Au(0)@Au(I)-硫醇核壳 NCs，其中 NC 表面的 Au(I)-硫醇配合物通过 AIE 产生强发光。我们能够将合成策略扩展到具有附加功能的其他硫醇配体（以定制设计的肽的形式）。这项研究中的发现（例如，确定发光的来源和发光中的尺寸效应）和合成方案可以为更好地理解这些新型发光探针和开发新的合成路线做出重大贡献。
