RESUMEN
Directional electron flow in the photocatalyst enables efficient charge separation, which is essential for efficient photocatalysis of H2 production. Here, we report a novel class of tetracationic cyclophanes (7) incorporating bipyridine Pt(II) and selenoviologen. X-ray single-crystal structures reveal that 7 not only fixes the distances and spatial positions between its individual units but also exhibits a box-like rigid electron-deficient cavity. Moreover, host-guest recognition phenomena are observed between 7 and ferrocene, forming host-guest complexes with a 1:1 stoichiometry in MeCN. 7 exhibits good redox properties, narrow energy gaps, and strong absorption in the visible range (370-500 nm) due to containing two selenoviologen (SeV2+) units. Meanwhile, the femtosecond transient absorption (fs-TA) reveals that 7 has stabilized dicationic biradical, efficient charge separation, and facilitates directional electron flow to achieve efficient electron transfer due to the formation of rigid cyclophane and electronic architecture. Then, 7 is applied to visible-light-driven hydrogen evolution with high hydrogen production (132 µmol), generation rate (11 µmol/h), turnover number (221), and apparent quantum yield (1.7%), which provides a simplified and efficient photocatalytic strategy for solar energy conversion.
RESUMEN
The novel selenoviologen-based tetracationic cyclophanes (green boxes 3 and 5) with rigid electron-deficient cavities are synthesized via SN2 reactions in two steps. The green boxes exhibit good redox properties, narrow energy gaps, and strong absorption in the visible range (370-470 nm), especially for the green box 5 containing two selenoviologen (SeV2+) units. Meanwhile, the femtosecond transient absorption (fs-TA) reveals that the green boxes have a stabilized dicationic biradical, high efficiency of intramolecular charge transfer (ICT), and long-lived charge separation state due to the formation of cyclophane structure. Based on the excellent photophysical and redox properties, the green boxes are applied to electrochromic devices (ECDs) and visible-light-driven hydrogen production with a high H2 generation rate (34 µmol/h), turnover number (203), and apparent quantum yield (5.33 × 10-2). In addition, the host-guest recognitions are demonstrated between the green boxes and electron-rich guests (e.g., G1:1-naphthol and G2:platinum(II)-tethered naphthalene) in MeCN through C-H···π and π···π interactions. As a one-component system, the host-guest complexes of green boxâG2 are successfully applied to visible-light photocatalytic hydrogen production due to the intramolecular electron transfer (IET) between platinum(II) of G2 and SeV2+ of the green box, which provides a simplified system for solar energy conversion.