The Green Box: Selenoviologen-Based Tetracationic Cyclophane for Electrochromism, Host-Guest Interactions, and Visible-Light Photocatalysis.

The novel selenoviologen-based tetracationic cyclophanes (green boxes and ) with rigid electron-deficient cavities are synthesized via S2 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 containing two selenoviologen (SeV) 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 H generation rate (34 μmol/h), turnover number (203), and apparent quantum yield (5.33 × 10). In addition, the host-guest recognitions are demonstrated between the green boxes and electron-rich guests (e.g., :1-naphthol and :platinum(II)-tethered naphthalene) in MeCN through C-H···π and π···π interactions. As a one-component system, the host-guest complexes of are successfully applied to visible-light photocatalytic hydrogen production due to the intramolecular electron transfer (IET) between platinum(II) of and SeV of the green box, which provides a simplified system for solar energy conversion.