Direct Imaging of “Patch-Clasping” and Relaxation in Robust and Flexible Nanoparticle Assemblies

Polymer patching on inorganic nanoparticles (NPs) enables multifunctionality and directed self-assembly into nonclosely packed optical and mechanical metamaterials. However, experimental demonstration of such assemblies has been scant due to challenges in leveraging patch-induced NP–NP attractions and understanding NP self-assembly dynamics. Here we use low-dose liquid-phase transmission electron microscopy to visualize the dynamic behaviors of tip-patched triangular nanoprisms upon patch-clasping, where polymer patches interpenetrate to form cohesive bonds that connect NPs. Notably, these bonds are longitudinally robust but rotationally flexible. Patch-clasping is found to allow highly selective tip–tip assembly, interconversion between dimeric bowtie and sawtooth configurations, and collective structural relaxation of NP networks. The integration of single particle tracking, polymer physics theory, and molecular dynamics simulation reveals the macromolecular origin of patch-clasping-induced NP dynamics. Our experiment–computation integration can aid the design of stimuli-responsive nanomaterials, such as topological metamaterials for chiral sensors, waveguides, and nanoantennas.