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.

A bioinspired polymer-based nanocomposite consisting of hierarchically oriented 2D nanomaterials and polymers exhibits extraordinary properties in various applications. However, it is still a great challenge to break through the limitations of the fabrication process and polymer types for producing a laminated nanocomposite with no restrictions in dimension. Herein, large-area bulk polypropylene carbonate (PPC)/polytetrahydrofuran-functionalized reduced graphene oxide (PTHF-fRGO) nanocomposites with nacre-like layered structures are fabricated through a cost-effective and large-scale evaporation-induced self-assembly process, followed by thermal laminating. To enhance the interfacial compatibility and self-assembly efficiency, the 2D RGO are noncovalently functionalized via controlled termination of living PTHF. The comprehensive properties of the laminated composites, including thermal, mechanical, shape memory, and gas barrier properties, can be significantly improved by introducing highly oriented RGO (<5 wt %). Tuning the composition of oriented RGO (>5 wt %) and PPC matrix in the laminated nanocomposite yields a material with high thermal and electrical conductivities and electromagnetic interference (EMI) shielding properties. Thus, the resulting high-performance and multifunctional PPC-based materials with potential biodegradability are potential replacements for petroleum-based plastics in various applications.