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Strong Visible-Light-Absorbing Cuprous Sensitizers for Dramatically Boosting Photocatalysis.

Kai-Kai ChenSong GuoHeyuan LiuXiyou LiZhi-Ming ZhangTong-Bu Lu
Published in: Angewandte Chemie (International ed. in English) (2020)
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)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 CuI complex and a backward triplet-triplet energy transfer greatly contribute to the long-lived and Bodipy-localized triplet excited state.
Keyphrases
  • energy transfer
  • visible light
  • quantum dots
  • aqueous solution
  • photodynamic therapy
  • metal organic framework
  • living cells
  • fluorescent probe
  • magnetic resonance imaging
  • computed tomography