Strong and Elastic Membranes via Hydrogen Bonding Directed Self‐Assembly of Atomically Precise Nanoclusters

Abstract 2D nanomaterials have provided an extraordinary palette of mechanical, electrical, optical, and catalytic properties. Ultrathin 2D nanomaterials are classically produced via exfoliation, delamination, deposition, or advanced synthesis methods using a handful of starting materials. Thus, there is a need to explore more generic avenues to expand the feasibility to the next generation 2D materials beyond atomic and molecular‐level covalent networks. In this context, self‐assembly of atomically precise noble nanoclusters can, in principle, suggest modular approaches for new generation 2D materials, provided that the ligand engineering allows symmetry breaking and directional internanoparticle interactions. Here the self‐assembly of silver nanoclusters (NCs) capped with p ‐mercaptobenzoic acid ligands (Na ₄ Ag ₄₄ ‐ p MBA ₃₀ ) into large‐area freestanding membranes by trapping the NCs in a transient solvent layer at air–solvent interfaces is demonstrated. The patchy distribution of ligand bundles facilitates symmetry breaking and preferential intralayer hydrogen bondings resulting in strong and elastic membranes. The membranes with Young's modulus of 14.5 ± 0.2 GPa can readily be transferred to different substrates. The assemblies allow detection of Raman active antibiotic molecules with high reproducibility without any need for substrate pretreatment.