Manipulation of Inorganic Atomic‐Layer Networks by Solution‐Phase Co‐assembly

Abstract

Homogeneous 2D lamellar assemblies of Au thiolate coordination polymer (ATCP) were obtained by two-ligand co-assembly. The orbital levels and the bandgap of the 2D Au -S network in the centre of the lamellae can be continuously tuned by means of the capping ligands on both sides, to give a new type of inorganic-organic composite semiconductor, the band structure of which can be easily tuned by low-temperature solution-phase co-assembly. Furthermore, the chemical reactivity of these ATCP co-assemblies also proved to be strongly dependent on the organic substituents, with well-tuneable transformation rates to gold nanoparticles. Apparently, this is the first work to demonstrate how organic substituents can continuously tune the electron band structure and chemical reactivity of inorganic atomic layers of semiconductor through co-assembly.

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 lamellar sheets have well‐resolved sharp UV‐vis absorption peaks, which are suggested to result from ligand‐to‐metal charge‐transfer (LMCT) and metal‐centered charge‐transfer (MCCT) transitions . Because the absorption peaks are very sensitive to the compositions of the assemblies, the change of UV‐vis spectrum was directly used to identify the compositional change.…”

“…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.…”

“…To construct such ah ighly dynamic reaction-coupled self-assembly system,i tn eeds at least two following conditions:f irst, the system should have enough complexity to show multiple stable/metastable structures so that it can adjust its structures amongt hesep ossible ones upon the environmental change; secondly, it should contain components to recognize the change of environments andr espond to it and lead to the change of structures.A fter years of studying on the self-assembly behavior of Au I -thiolate coordination polymer,w er ealize that it is very promising for it to develop into ah ighly dynamic system to construct unprecedented complex structuresa nd show environmental adaptions. [37][38][39][40][41][42] The uniquenesso fA u I -thiolate includes:i )itc an achieve double-ligandc o-assemblies with well tunable compositions and show severalp seudo-polymorphs, suggesting the excellent structural tailorability; [40,41] ii)the synthesis of Au I -thiolate is accompanied with at hiol to disulfideo xidation reaction, making the reaction coupled selfassemblyp ossible. Here, by manipulatingt he pH-dependent thiol-disulfide exchange [43][44][45] between two ligands, it triggered the subsequentl igand exchange in Au I -thiolate and resulted in ah ighly dynamic assembly process, in which the compositions of the assemblies continuouslyc hanged with time.…”