Tailoring Anisotropic Interactions between Soft Nanospheres Using Dense Arrays of Smectic Liquid Crystal Edge Dislocations

We investigated composite films of gold nanoparticles (NPs)/liquid crystal (LC) defects as a model system to understand the key parameters, which allow for an accurate control of NP anisotropic self-assemblies using soft templates. We combined spectrophotometiy, Raman spectroscopy, and grazing incidence small-angle X-ray scattering with calculations of dipole coupling models and soft sphere interactions. We demonstrate that dense arrays of elementary edge dislocations can strongly localize small NPs along the defect cores, resulting in formation of parallel chains of NPs. Furthermore, we show that within the dislocation core the inter-NP distances can be tuned. This phenomenon appears to be driven by the competition between "soft (nano)sphere" attraction and LC-induced repulsion. We evidence two extreme regimes controlled by the solvent evaporation: (i) when the solvent evaporates abruptly, the spacing between neighboring NPs in the chains is dominated by van der Waals interactions between interdigitated capping ligands, leading to chains of close-packed NPs; (ii) when the solvent evaporates slowly, strong interdigitation between the is avoided, leading to a dominating LC-induced repulsion between NPs associated with the replacement of disordered cores by NPs. The templating of NPs by topological defects, beyond the technological inquiries, may enable creation, investigation, and manipulation of unique collective features for a wide range of nanomaterials.