Strong Visible‐Light‐Absorbing Cuprous Sensitizers for Dramatically Boosting Photocatalysis. Issue 31 (20th May 2020)

• Record Type: Journal Article
• Authors: Chen, Kai‐Kai; Guo, Song; Liu, Heyuan; Li, Xiyou; Zhang, Zhi‐Ming; Lu, Tong‐Bu
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 31(2020)
• Page Start: 12951
• Page End: 12957
• Publication Date: 2020-05-20
• Subjects: copper -- light harvesting -- oxidation -- photosensitizers -- photocatalysis; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202003251
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Developing strong visible‐light‐absorbing (SVLA) earth‐abundant photosensitizers (PSs) for significantly improving the utilization of solar energy is highly desirable, yet it remains a great challenge. Herein, we adopt a through‐bond energy transfer (TBET) strategy by bridging boron dipyrromethene (Bodipy) and a Cu I complex with an electronically conjugated bridge, resulting in the first SVLA Cu I PSs (Cu‐2 and Cu‐3 ). Cu‐3 has an extremely high molar extinction coefficient of 162 260 m −1 cm −1 at 518 nm, over 62 times higher than that of traditional Cu I PS (Cu‐1 ). The photooxidation activity of Cu‐3 is much greater than that of Cu‐1 and noble‐metal PSs (Ru(bpy)3 2+ and Ir(ppy)3 + ) for both energy‐ and electron‐transfer reactions. Femto‐ and nanosecond transient absorption and theoretical investigations demonstrate that a "ping‐pong" energy‐transfer process in Cu‐3 involving a forward singlet TBET from Bodipy to the Cu I complex and a backward triplet‐triplet energy transfer greatly contribute to the long‐lived and Bodipy‐localized triplet excited state. Abstract : Harvest home : Through‐bond energy transfer (TBET) strategy was employed to construct a low‐cost copper(I) photosensitizer (PS) with high visible‐light harvesting ability and a long‐lived excited state. For energy‐ and electron‐transfer reactions it dramatically outperforms traditional Cu‐PS and noble‐metal PSs (Ru(bpy)3 2+ and Ir(ppy)3 + ).