Harnessing Exciton Flux With a Single‐Stranded DNA‐Programmed Nanodevice

Natural and artificial nanosystems rely on functional module assembly, yet overcoming thermodynamic incompatibility in atomically precise nanodevice integration remains challenging. Here, we construct a single-stranded DNA (ssDNA)-directed nanodevice that achieves 94.3% quenching efficiency by harnessing asymmetric π-π interactions to split exciton energy levels. DNA spatial confinement orchestrates hydrophobic, covalent, and π-π interactions, enabling precise component arrangement. This nanodevice comprises a light-harvesting engine, a vibrational metal nanocluster actuator and a programmable ssDNA. Asymmetric π-π interactions between fluorophore and metal nanocluster in DNA spatial confinements split fluorophore energy levels, directing exciton flux. Complementary DNA strands modulate engine-actuator coupling, enabling enthalpy-driven switching between radiative and non-radiative pathways. By tuning DNA length and nanocluster ligands, we achieve continuous control over energy transfer efficiency. This programmable platform, manipulating non-radiative decay via π-π interactions, establishes vibrational control as a general paradigm for nanoscale energy transduction.