Sterically Programmed Dynamic‐Covalent Self‐Assembly Enables High‐Throughput Engineering of Supramolecular Nanotubes

ABSTRACT Supramolecular self‐assembly provides an attractive route to organic semiconducting nanotubes, yet concurrent control over tube diameter, helicity and wall number remains elusive. Here we report a dynamic‐covalent strategy that converts a single perylene diimide aldehyde precursor (PDIOA) into a family of nanotubes through one‐pot imine formation with small amines. Combining microscopy, diffraction and DFT analysis, we show that steric congestion at the ortho position programs a helical packing mode that nucleates and propagates tubular architectures. Crucially, the nanotube inner diameter can be predictably “dialled” by the steric demand of the amine: increasing steric bulk progressively contracts the tube cavity. Enantiomeric amines further translate molecular chirality into opposite supramolecular helicities, affording mirror‐image helical nanotubes. Moreover, tuning monomer concentration and solvent composition enables uniform double‐ and triple‐walled nanotubes, demonstrating controllable wall‐layer engineering within the same chemical platform. The resulting nanotubes exhibit dimension‐dependent photoconductive responses, linking programmable nanoscale structure to optoelectronic function. This work establishes a modular, high‐throughput and recyclable route to chiral, multiwalled perylene diimide nanotubes with independently addressable diameter, helicity and wall number.