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 (M_w) of the polymer ligands and the size of the GNRs. By increasing M_w 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 M_w 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.