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Most of all‐fused‐ring π‐conjugated molecules have wide or medium bandgap and show photo response in the visible range. In this work, an all‐fused‐ring n‐type molecule, which exhibits an ultrasmall optical bandgap of 1.22 eV and strong near‐infrared (NIR) absorption with an onset absorption wavelength of 1013 nm is reported. The molecule consists of 14 aromatic rings and has electron donor–acceptor...