Affiliation:
1. Frontier Institute of Science and Technology State Key Laboratory for Strength and Vibration of Mechanical Structures Xi'an Key Laboratory of Electronic Devices and Material Chemistry Engineering Research Center of Key Materials for Efficient Utilization of Clean Energy of Shaanxi Province Future Industrial Innovation Institute of Emerging Information Storage and Smart Sensor Xi'an Jiaotong University Xi'an Shaanxi Province 710054 P. R. China
2. School of Materials Science and Engineering Chang'an University Xi'an Shaanxi Province 710064 P. R. China
3. School of Materials Science and Engineering Northwestern Polytechnical University Xi'an Shaanxi Province 710072 P. R. China
Abstract
AbstractDirectional 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.