Size-selective 2D ordering of gold nanoparticles using surface topography of self-assembled diamide template

Size-selective organization of ~2 nm dodecanethiol stabilized gold nanoparticles (AuNPs) into periodic 1D arrays by using the surface topographical features of a soft template is described. The template consists of micrometer length nanotapes organized into nanosheets with periodic valleys running along their length and is generated by the hierarchical self-assembly of a diamide molecule (BHPB) in cyclohexane. The AuNP ordering achieved simply by mixing the preformed template with the readily available ~2 nm dodecanethiol stabilized AuNPs is comparable to those obtained using programmable DNA and functional block copolymers. The observed periodicity of the AuNP arrays provided valuable structural clues about the organization of nanotapes into nanosheets. Self-assembling BHPB molecules in the presence of AuNPs by heating and cooling the two components led to a comparatively disordered organization because the template structure was changed under these conditions. Moreover, the template could not order larger AuNPs (~5 nm) into a similar 1D array, owing to the steric restriction imposed by the dimension of the valleys on the template. Interestingly, this geometric constraint led to AuNP size sorting when a polydisperse sample (2.5 ± 0.9 nm) was used for organization, with AuNPs attached to the template edges being larger (≥2.2 ± 0.9 nm) than those associated to the inner valleys (1.6 ± 0.8 nm). This is a unique example of size-sorting induced by the surface topographical features of a soft template.