Effect of rhodamine 6G dye molecular interactions on counterintuitive self-assembly of noble metal nanorods

Hypothesis: Self-assembled nanostructures with highly ordered and diversified patterns can be obtained by adding additives that directionally control the interparticle interactions. However, due to the complex non-covalent weak interactions in the self-assembly process, the active mechanism of additives is not fully understood, resulting in the limitation of obtaining the nano-superstructures. The introduction of rhodamine 6G (R6G) enables gold nanorods (GNRs) self-assembled into a counterintuitive tetragonal superlattice, during which the exploration of the influence of R6G molecular interactions on the GNRs self-assembly is of importance. Experiments: We present the detailed investigations of spacial configuration, binding modes, and aggregated degree of R6G molecule on formation of the tetragonal GNRs superlattices by combining the experimental and simulated results. Findings: By analyzing the peak position and peak intensity in the fluorescent spectra of assembled samples and pure R6G samples, H-dimer is verified as the main cause for inducing the tetragonal superstructures. Molecular dynamics simulations reveal that 2–3 H-dimers adsorbed obliquely in a zigzag chain manner on the surface of GNRs is the most stable state of the self-assembly. This work would contribute to a deeper understanding of the complex colloidal nanoparticle self-assemblies and push forward the development of the bottom-up nanoscale superstructures.