Solvent-induced stable pseudopolymorphism of Au(i)–thiolate lamellar assemblies: a model system for understanding the environment acclimation of biomacromolecules

Abstract

Two pseudopolymorphs are achieved in two solvents and exhibit high structure preservation but have distinct optical properties, morphology and thermal stability.

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

“…The synthesis of Au I ‐thiolate is through the reaction of Au III ions and thiol ligands in aqueous phase at boiling temperature . Au III ions were first reduced by thiol ligands to Au I and then coordinated with the residual thiol ligands to form linear coordination polymer chains instantly [equation (1)].…”

“…The synthesis of Au I -thiolate is through the reaction of Au III ions and thiol ligandsi na queous phase at boiling temperature. [37][38][39][40][41][42] Au III ions were first reduced by thiol ligands to Au I [a] S.…”

“…After years of studying on the self‐assembly behavior of Au I ‐thiolate coordination polymer, we realize that it is very promising for it to develop into a highly dynamic system to construct unprecedented complex structures and show environmental adaptions . The uniqueness of Au I ‐thiolate includes: i) it can achieve double‐ligand co‐assemblies with well tunable compositions and show several pseudo‐polymorphs, suggesting the excellent structural tailorability; ii) the synthesis of Au I ‐thiolate is accompanied with a thiol to disulfide oxidation reaction, making the reaction coupled self‐assembly possible. Here, by manipulating the pH‐dependent thiol‐disulfide exchange between two ligands, it triggered the subsequent ligand exchange in Au I ‐thiolate and resulted in a highly dynamic assembly process, in which the compositions of the assemblies continuously changed with time.…”

Self‐Templated Assembly of AuI/AgI‐Thiolate Sheets with Central Holes

“…Component of Au I ‐thiolate was synthesized by reaction of HAuCl 4 with excess MPA‐Na (4 equivalents) in water at room temperature. Two equivalents of thiols first reduce Au III to Au I and then the remaining thiols coordinate with Au I to form Au I ‐thiolate . In contrast to the Ag I ‐thiolate, Au I ‐thiolate monomers/oligomers (Au I ‐thiolate‐Mono‐/Oligomer) forms amorphous string‐like intermediates which are very small and nearly invisible in TEM images (Au I ‐thiolate‐Strings, yield by dialysis: ≈100 %, Figure S2 a,f).…”

“…Twoe quivalents of thiols first reduce Au III to Au I and then the remaining thiols coordinatew ith Au I to form Au Ithiolate. [30][31][32][33][34][35] In contrastt ot he Ag I -thiolate, Au I -thiolate monomers/oligomers (Au I -thiolate-Mono-/Oligomer) forms amorphous string-like intermediates which are very small andn early invisible in TEM images [34] (Au I -thiolate-Strings, yield by dialysis: % 100 %, Figure S2 a,f). Au I -thiolate-Strings further grow longer, aggregate and crystallize to form sheetsatboilingtemperature (Au I -thiolate-Sheets, separation yield by centrifugation: % 80 %, Figure 1h,S 2b-f).…”