Strong Visible‐Light‐Absorbing Cuprous Sensitizers for Dramatically Boosting Photocatalysis

다국어 초록 (Multilingual 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 CuI complex with an electronically conjugated bridge, resulting in the first SVLA CuI 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 CuI PS (Cu‐1). The photooxidation activity of Cu‐3 is much greater than that of Cu‐1 and noble‐metal PSs (Ru(bpy)32+ 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 CuI complex and a backward triplet‐triplet energy transfer greatly contribute to the long‐lived and Bodipy‐localized triplet excited state.
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)32+ and Ir(ppy)3+).