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

作者：Naiyao Li, Yawen Li, Zengrong Wang, Tianle Cao, Chenjing Liu, Hongyue Wang, Guoping Li, Gang He · 发表于：Angewandte Chemie International Edition · 年份：2024 · DOI：10.1002/anie.202410525 · 被引用次数：11 · 研究领域：Porphyrin and Phthalocyanine Chemistry、Electrocatalysts for Energy Conversion、CO2 Reduction Techniques and Catalysts

Abstract 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.