Hydrogen‐Bond‐Induced Switching of Interaction Hierarchy in Dipolar D–A Chromophores for NIR Circularly Polarized Photodetection

Dipolar donor-acceptor (D-A) chromophores exhibit strong near-infrared (NIR) absorption but are intrinsically biased toward electrostatically complementary hetero-association-a packing mode that inherently suppresses chiroptical responses. Here, we show that this preference can be overcome through hydrogen-bond-induced switching of the interaction hierarchy governing supramolecular assembly. In croconaine-based dipolar D-A chromophores, the introduction of directional amide-mediated hydrogen bonding establishes a thermodynamically favored homo-association that overrides dipolar complementarity, thereby switching the preferred packing mode from hetero- to homo-organization. This interaction hierarchy switching drives cooperative homochiral assembly and enables amplified NIR chiroptical responses. Integration of these assemblies into heterojunction devices translates the supramolecular structural reorganization into helicity-dependent electrical outputs, affording efficient NIR circularly polarized photodetection. These results identify interaction hierarchy inversion as an effective strategy for controlling association modes and chiroptical functions in dipolar chromophores.