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Strong Visible‐Light‐Absorbing Cuprous Sensitizers for Dramatically Boosting Photocatalysis
Author(s) -
Chen KaiKai,
Guo Song,
Liu Heyuan,
Li Xiyou,
Zhang ZhiMing,
Lu TongBu
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202003251
Subject(s) - photochemistry , bodipy , photocatalysis , ultrafast laser spectroscopy , electron transfer , excited state , chemistry , singlet state , visible spectrum , molar absorptivity , conjugated system , photon upconversion , materials science , fluorescence , catalysis , optoelectronics , doping , atomic physics , laser , biochemistry , physics , polymer , organic chemistry , quantum mechanics , optics
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.