Dynamic self-assembly of silver nanoclusters into luminescent nanotubes with controlled surface roughness: Scaffold of superhydrophobic materials

•Nanotubes with rough surfaces were obtained through the self-assembly of Ag6-NCs/PEI.•The luminescence of Ag6-NCs enhanced sharply based on AIE.•The nanotubes possess superhydrophobicity and can suppress “coffee-ring” effects. Self-assembly of metal nanoclusters (NCs) have shown applicability, while the types of the structures of NCs aggregates are still limited. Proper control of the pathway complexity for supramolecular self-assembly process is the key to fabricate ideal supramolecular structures. Herein, the multi-pathway co-assembly of silver NCs [Ag6(mna)6] (NH4)6 (Ag6-NCs) with polyethyleneimine (PEI) into diverse nanostructures were systematically studied. Nanotubes with rough surfaces were obtained as following: kinetically trapped metastable nanoparticles formed firstly and transform into thermodynamically favored fibers. Subsequently, the fibers could breakup into nanotubes through “top-down” sculpture. These phenomena have rarely been reported in the field of nanoclusters self-assembly. Furthermore, the Ag6-NCs/PEI nanotubes were found to be a versatile material with aggregation-induce emission (AIE) in aqueous solution that the fluorescence of Ag6-NCs enhanced sharply with the formation of nanotubes owing to the formation of ordered nanotubes which suppress the ligand vibration and block energy loss of nonradiative decay. More importantly, the rough surface and anisotropic structure endow them potential application for fabrication of superhydrophobic surfaces and suppression of “coffee-ring” effects.