Kinetic Study on the Self-Assembly of Au(I)-Thiolate Lamellar Sheets: Preassembled Precursor vs Molecular Precursor

J Phys Chem A. 2018 Jun 14;122(23):5089-5097. doi: 10.1021/acs.jpca.8b02103. Epub 2018 Jun 4.

Abstract

Molecular self-assembly has played an important role in nanofabrication. Due to the weak driving forces of noncovalent bonds, developing molecular nanoassemblies that have both robust preparation conditions and stable structure is a challenge. In our previous work, we have developed a reversible self-assembly system of Au(I)-thiolate coordination polymer (ATCP) to form colloidal lamellar sheets and demonstrated the high tailorability and stability of their structures, as well as their promising applications in gold nanocluster/nanoparticle fabrication and UV light shielding. Here, we first reported our progress in exploring a robust and green assembly protocol toward ATCP colloidal lamellar sheets in water by allowing the molecular precursors of HAuCl4 and the thiol ligand to form ATCP preassembled intermediates. In this way, colloidal ATCP lamellar sheets can be prepared in a wide range of synthetic concentrations ([Au]0 ≥ 2 × 10-4 M) and at broad assembly temperatures (80-100 °C) with similar high yields (>80%). The assembly kinetics at different conditions are also studied in detail to help understand the robust assembly process. The robust and green synthetic protocols will pave a way for their real applications.