Meticulous surface patterning of nanoparticles with anisotropic patches as analogs of functional groups offers fascinating potential in many fields, particularly in controllable materials assembly. However, patchy colloids generally evolve into high-symmetry solid structures, mainly because the assembly interactions arise between patches via patch-to-patch recognition. Here, we report an assembly concept, that is, a soft patch, which enables selective and directional fusion of liquid droplets for producing highly asymmetrical hollow nanospacecrafts. Our approach enables precise control of hollow nanoparticle diameters by manipulating droplet fusion regions. By controlling the patch number, more orientations are accessible to droplet fusion, allowing for increased degrees of complexity of hollow self-assemblies. The versatility and curvature-selective growth of this strategy are demonstrated on three nonspherical nanoparticles, enabling the creation of highly asymmetric nanospacecrafts. By patterning Au-core Ag-shell nanorods, the nanospacecraft can be programmed in response to either H2O2 or near-infrared light, exhibiting dual-mode response behavior with a 208% increase in the diffusion coefficient in both modes compared with other nanoscale low-asymmetry active materials. Overall, these findings are a significant step toward designing new patch interactions for materials self-assembly for creating complex hollow colloids and functional nanodevices that are otherwise inaccessible.

https://doi.org/10.1021/jacs.2c01096