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

Abstract

The novel selenoviologen-based tetracationic cyclophanes (green boxes 3 and 5 ) with rigid electron-deficient cavities are synthesized via S N 2 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 (SeV 2+ ) 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 2 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 box⊃G2 are successfully applied to visible-light photocatalytic hydrogen production due to the intramolecular electron transfer (IET) between platinum(II) of G2 and SeV 2+ of the green box, which provides a simplified system for solar energy conversion.