Self-assembly of water-soluble silver nanoclusters: superstructure formation and morphological evolution

Supramolecular self-assembly, based on non-covalent interactions, has been employed as an efficient approach to obtain various functional materials from nanometer-sized building blocks, in particular, [Ag₆(mna)₆]^6-, mna = mercaptonicotinate (Ag₆-NC). A challenging issue is how to modulate the self-assembly process through regulating the relationship between building blocks and solvents. Herein, we report the controlled self-assembly of hexanuclear silver nanoclusters into robust multilayer vesicles in different solvents, DMSO, CH₃CN, EG and MeOH. Their unique luminescence enables them to be bifunctional probes to sense Fe³⁺ and dl-dithiothreitol (DTT). By protonating the Ag₆-NC to Ag₆-H-NC using hydrochloric acid (HCl), the multilayer vesicles survive in aprotic solvents, DMSO and CH₃CN, but are transformed to nanowires in protic solvents, water, EG and MeOH. Our results demonstrated that the solvent-bridged H-bond plays a key role in the evolution of the morphologies from vesicles to nanowires. Moreover, the nanowires could further hierarchically self-assemble in water into hydrogels with high water content (99.5%), and with remarkable mechanical strength and self-healing properties. This study introduces a robust cluster-based building block in a supramolecular self-assembly system and reveals the significance of aprotic and protic solvents for the modulation of the morphologies of cluster-based aggregates.