Reactions Coupled Self‐ and Co‐Assembly: A Highly Dynamic Process and the Resultant Spatially Inhomogeneous Structure

Abstract

Reactions coupled self‐assembly represents a step forward towards biomimetic behavior in the field of supramolecular research. Here, two pH‐dependent reactions of thiol‐disulfide exchange and ligand exchange were used to couple with the self‐assembly of an AuI‐thiolate coordination polymer consisting of two ligands. Thanks to the comparable rates between the reactions and self‐assembly, the compositions of the assemblies change continuously with time, resulting in a highly dynamic assembly process and spatially inhomogeneous structure that are very common in life systems but cannot be easily obtained with one‐pot artificial methods.

A Study on Au(I)‐thiolate Nanosheets as Water‐dispersible UV Absorbents

“…Although there are still remaining sheets that links the nanoparticles as seen in Au(I)−MPA and Au(I)−MPA−GSH, the generated nanoparticles within them have greatly break the continuous 2D coordination network, therefore the absorption are greatly reduced. The results are in agreement with our previous conclusion that the strong absorption for Au(I)‐thiolates is closely related to the 2D structure with strong aurophilic interactions, while the 1D preassemblies or the dissembled products will greatly reduce the strong absorption [32] …”

“…First, thiol reduces Au(III) to Au(I), then the remaining thiol ligands coordinate with Au(I) to form linear Au(I)‐thiolate chains. The linear Au(I)‐thiolate chains further pack side‐by‐side by aurophilic and inter ligand interactions to form string shaped preassemblies, and the preassemblies aggregate and fuse to form nanosheets (Figure 1a) [31–33] . Due to the strong aurophilic interactions, the assemblies have sharp and narrow absorption bands in 200–400 nm region (Figure S1) [31] .…”

“…Due to the strong aurophilic interactions, the assemblies have sharp and narrow absorption bands in 200–400 nm region (Figure S1) [31] . By changing the type of ligands and ligand compositions, the absorption peaks can be continuously tuned [32] . Herein, we selected two single‐ligand assemblies (Au(I)−MPA, λ=392 nm, Au(I)−Cys, λ=355 nm) and two dual‐ligand co‐assemblies (Au(I)−MPA−GSH, λ=380 nm, Au(I)−MPA−Cys, λ=360 nm) to study their potentials as UV absorbents.…”

“…The linear Au(I)-thiolate chains further pack side-by-side by aurophilic and inter ligand interactions to form string shaped preassemblies, and the preassemblies aggregate and fuse to form nanosheets (Figure 1a). [31][32][33] Due to the strong aurophilic interactions, the assemblies have sharp and narrow absorption bands in 200-400 nm region ( Figure S1). [31] By changing the type of ligands and ligand compositions, the absorption peaks can be continuously tuned.…”

“…Au(I)-thiolate nanosheets are assembled from linear Au(I)thiolate coordination polymers through side by side aurophilic interactions, and inter-ligand hydrogen bonds and hydrophobic interactions. [31][32] After self-assembled, the nanosheets show strong absorption bands at 200-400 nm from charge transfer from ligand to metal and among the metal centers, covering both UVA and UVB regions. By changing the types of ligands, the absorption positions can be continuously tuned.…”