ABSTRACT 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.
Duan et al. (2026) studied this question.