Photochromic Semiconductive Hydrogen-Bonded Organic Framework (HOF) with Broadband Absorption

Semiconductors with broadband photoelectric response have important practical needs in many aspects such as solar energy conversion, photocatalysis, and photodetection. We synthesized the first photochromic semiconductive hydrogen-bonded organic framework (HOF), [H₂(bpyb)](H₂PO₄)₂·2H₂O (1), using the polycyclic viologen cation [H₂(bpyb)] (bpyb = 1,4-bis(tetrapyridyl)benzene). After 1 s of xenon lamp irradiation, compound 1 showed a visible color change from the initial yellowish to dark purple after continuous irradiation. The photoinduced radical product has an absorption band covering 200-1700 nm, which is wider than the absorption ranges of silicon and perovskites. It produced photocurrent when irradiated with a xenon lamp or a laser (355, 532, or 808 nm). The on/off ratio of the current (I_irr/I_dark) can be as high as 300 times under the irradiation of the 808 nm laser with a power of 1.9 W cm^-2. In addition, under the 808 nm light source, the on/off ratio of 1B is 35 times that of 1A.