Efficient One-Pot Synthesis and pH-Dependent Tuning of Photoluminescence and Stability of Au₁₈(SC₂H₄CO₂H)₁₄ Cluster

Developing efficient ways to control the nanocluster properties and synthesize atomically precise metal nanoclusters are the foremost goals in the field of metal nanocluster research. In this article, we demonstrate that the direct synthesis of atomically precise, hydrophilic metal nanoclusters as well as tuning of their properties can be achieved by an appropriate selection of reactants, binding ligand, and their proportions. Thus, a facile, single-step method has been developed for the direct synthesis of Au₁₈(SC₂H₄CO₂H)₁₄ nanocluster in an aqueous medium under ambient conditions. The synthesis does not require any pH or temperature control and postsynthesis size-separation step. The use of a hydrophilic, bifunctional short carbon-chain capping ligand, HSC₂H₄CO₂H, allows tuning of cluster properties such as the photoluminescence and stability in an aqueous medium via the variation of pH of the cluster solution. By using a phase transfer catalyst, the nanoclusters can also be transferred into toluene solvent, which further enhances the nanocluster photoluminescence. The formation, composition, and purity of the product clusters have been characterized by using a number of methods such as the polyacrylamide gel electrophoresis, UV-visible and FTIR spectroscopies, transmission electron microscopy, energy dispersive X-ray analysis, thermogravimetric analysis, X-ray photoelectron spectroscopy, and matrix-assisted laser desorption ionization-time-of-flight mass spectrometry. Gold nanoclusters with properties such as water solubility, water-to-organic phase-transfer ability, and tunable stability and photoluminescence are promising for various studies and applications. The work reveals a few principles that can be helpful in the development of a general toolbox for the rational design of size-selective synthesis and properties tuning of the metal nanoclusters.