Directional Electron Flow in a Selenoviologen‐Based Tetracationic Cyclophane for Enhanced Visible‐Light‐Driven Hydrogen Evolution

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. 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.