摘要： Extending photoresponse ranges of semiconductors to the entire ultraviolet–visible (UV)–shortwave near-infrared (SWIR) region (ca. 200–3000 nm) is highly desirable to reduce complexity and cost of photodetectors or to promote power conversion efficiency of solar cells. The observed up limit of photoresponse for organic-based semiconductors is about 1800 nm, far from covering the UV–SWIR region. Here we develop a cyanide-bridged layer-directed intercalation approach and obtain a series of two viologen-based 2D semiconductors with multispectral photoresponse. redox-active N-methyl bipyridinium cations with near-planar structures are sandwiched by cyanide-bridged MnII–FeIII or ZnII–FeIII layers. Radical–π interactions among the infinitely π-stacked N-methyl bipyridinium components favor the extension of absorption range. Both semiconductors show light/thermo-induced color change with the formation of stable radicals. They have intrinsic photocurrent response in the range of at least 355–2400 nm, which exceeds all reported values for known single-component organic-based semiconductors.