Self-Assembly of Polymer End-Tethered Gold Nanorods into Two-Dimensional Arrays with Tunable Tilt Structures

We demonstrated a facile yet effective strategy for self-assembly of polymer end-tethered gold nanorods (GNRs) into tunable two-dimensional (2D) arrays with the assistance of supramolecules of hydrogen bonded poly(4-vinyl pyridine) (P4VP) and 3-n-pentadecylphenol (PDP). Well-ordered 2D arrays with micrometer size were obtained by rupturing the assembled supramolecular matrix with a selective solvent. The formation of long-range ordered 2D arrays during a drying process was observed via small-angle X-ray scattering. Interestingly, the packing structure of the ordered arrays strongly depends on the molecular weight (Mw) of the polymer ligands and the size of the GNRs. By increasing Mw of the polymer ligands, tilted arrays can be obtained. The average angle between GNRs and the surface normal direction of the layered 2D arrays changes from 0 to 37° with the increase in Mw of the polymer ligands. A mechanism for assembly behavior of dumbbell shapes with a soft shell structure has been proposed. The resulting GNR arrays with different orientations showed anisotropic surface-enhanced Raman scattering (SERS) performance. We showed that the vertically ordered GNR arrays exhibited ∼3 times higher SERS signals than the tilt ordered arrays. The results prove that the polymer end-tethered GNRs can be used as a building block for preparing the tilted 2D arrays with tunable physicochemical properties, which could have a wide range of potential applications in photonics, electronics, plasmonics, etc.