Highly Stable Triangular Single-Layer 2D Assemblies: Synthesis and Their Stimuli-Responsive Elastic and Anisotropic Curling.

Synthesis of highly stable two-dimensional single-layer assemblies (SLAs) is a key challenge in supramolecular science, especially those with long-range molecular order and well-defined morphology. Here, thin (thickness <2 nm) triangular AuI -thiolate SLAs with high thermo-, solvato- and mechano- stability have been synthesized via a double-ligand co-assembly strategy. Furthermore, the SLAs show assembly-level elastic and anisotropic deformation responses to external stimuli as a result of the long-range anisotropic molecular packing, which provides SLAs with new application potentials in bio-mimic nanomechanics.

Three-ligand Co-assembled 2D Au(I)-Thiolate Nanosheets.

Two-dimensional (2D) Au(I)-thiolate assemblies are a special type of material that can balance high structural stability and rich surface functionality, which shows promising prospects in both fundamental research and applications. Co-assembly of multiple ligands is a facile way to further enrich the surface properties and functions, and expand their application potentials. In this work, taking 3-mercaptopropionic acid (MPA), cysteine (Cys) and 1-thioglycerol (TGO) as example ligands, we studied in detail the possibility to co-assemble them into one nanosheet. Although the three ligands have significantly different controllability and pathways when self-assembling individually with Au(I), they can still be effectively co-assembled by reacting with HAuCl4 together to obtain three-ligand nanosheets with good colloidal stability. The key points for successful co-assembly are also revealed by comparing single- and three-ligand self-assembly processes, laying a solid foundation for co-assembly of even more ligands. The easy but powerful strategy for 2D materials with closely-packed and multiple tunable surface functional groups addresses the surface engineering problem for 2D materials and paves the way for their wider applications in sensing and biomaterials.

Wide-Range and Highly Sensitive Chiral Sensing by Discrete 2D Chirality Transfer on Confined Surfaces of Au(I)-Thiolate Nanosheets.

Circular dichroism (CD) chiral sensing is very promising to meet the ever-increasing demands for high-throughput chiral analysis in asymmetric synthesis. However, it is still very challenging to sensitively quantify the composition of enantiomers in a wide concentration range because the existing sensing systems show either linear CD response resultant from stoichiometric chiral transfer or nonlinear CD response resultant from amplified chiral transfer and thus have the drawbacks of low sensitivity and narrow quantification range, respectively. Herein, we propose a sensing system of two-dimensional (2D) Au(I)-thiolate nanosheets. The disordered interligand interactions on the confined surfaces of nanosheets enable the formation of discrete amplified chiral domains around the adsorbed chiral analytes, resulting in a linearly amplified chiral transfer behavior, which provides a solution for highly sensitive and wide-range quantification of enantiomer compositions. Taking (1R, 2R)-(-)- and (1S, 2S)-(+)-1,2-diamino cyclohexanes as example analytes, the concentration and full-range enantiomeric excess (ee) values have been quickly determined by adsorbing them on the surface of Au(I)-MPA (MPA: 3-mercaptopropionic acid) nanosheets in the concentration range of 1.0 × 10-6 to 4.0 × 10-5 M. By engineering the surface functional groups, Au(I)-thiolate nanosheets can be extended to sense other types of analytes, and several polyols with multiple chiral centers have been sensed by boronic acid functionalized nanosheets at the 10-7 M level. The high performances, good extendibility, and one-pot high-yield aqueous synthesis ensure these Au(I)-thiolate nanosheets can be developed as a practical and powerful chiral sensing platform.

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

Composite crystalline sheets of AuI /AgI -thiolate with central holes are achieved by co-assembly of AgI -thiolate and AuI -thiolate in one-pot without sacrificial template. Both AgI -thiolate and AuI -thiolate can separately assemble to lamellar sheets with similar structures, which makes their co-assembly possible, while the differences in their assembly pathways make the co-assembly processes highly dynamic and complex. First, a core@shell structure with AgI -thiolate at the core was formed upon the mixing of the two, then the core@shell structure transformed to a hole@shell structure by dissociation of the core. Finally, some instable hole@shell structures further dissociated and grew on stable ones to generate holed AuI /AgI -thiolate composite sheets, in which the two components neither have severe phase separation nor blend uniformly at atomic level. By tuning the feeding ratios, the average diameter of the holes can be controlled. Therefore, the work demonstrates the advantage of co-assembly technique in obtaining complex structurers. The holed sheets can further assemble to porous macroscopic materials and transform to composite metal nanoparticles by pyrolysis.

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

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.