Exploring the Chiroptical Engineering in Free Space Encoded with DNA‐Assembled Plasmonic Hybrids of Isotropic/Anisotropic Objects

ABSTRACT Spatial chirality programming in plasmonic nanostructures is essential to overcome fundamental limitations of conventional chiral photonics, yet persistent symmetry constraints intrinsically restrict programmable chiroptical control. Here, we employ DNA origami to construct hybrid plasmonic systems integrating gold nanocubes (NCs) or nanospheres (NSs) with nanorods (NRs). We demonstrate that NC‐NR hybrids exhibit robust, angle‐tunable ( θ ) 3D circular dichroism (3D‐CD) responses featuring reversible sign inversion, whereas geometrically isotropic NS‐NR counterparts show negligible chirality. This chiral mechanism arises from wavelength‐dependent phase reversal and incident‐direction‐encoded coupling of plasmon modes, where the longitudinal and transverse modes of the nanorods hybridize with multiple nanocube modes, collectively governing the dual‐band (680 and 540 nm) 3D‐CD responses. This work establishes and validates a programmable platform for spatial chiroptical engineering.