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Broadband and strong visible-light-absorbing cuprous sensitizers for boosting photosynthesis.

Kai-Kai ChenChao-Chao QinMeng-Jie DingSong GuoTong-Bu LuZhi-Ming Zhang
Published in: Proceedings of the National Academy of Sciences of the United States of America (2022)
Rational construction of broadband and strong visible-light-absorbing (BSVLA) earth-abundant complexes is of great importance for efficient and sustainable solar energy utilization. Herein, we explore a universal Cu(I) center to couple with multiple strong visible-light-absorbing antennas to break the energy level limitations of the current noble-metal complexes, resulting in the BSVLA nonprecious complex ( Cu-3 ). Systematic investigations demonstrate that double "ping-pong" energy-transfer processes in Cu-3 involving resonance energy transfer and Dexter mechanism enable a BSVLA between 430 and 620 nm and an antenna-localized long-lived triplet state for efficient intermolecular electron/energy transfer. Impressively, Cu-3 exhibited an outstanding performance for both energy- and electron-transfer reactions. Pseudo-first-order rate constant of photooxidation of 1,5-dihydroxynaphthalene with Cu-3 can achieve a record value of 190.8 × 10 - 3 min - 1 among the molecular catalytic systems, over 30 times higher than that with a noble-metal photosensitizer (PS) [Ru(bpy) 3 ] 2+ . These findings pave the way to develop BSVLA earth-abundant PSs for boosting photosynthesis.
Keyphrases
  • energy transfer
  • visible light
  • quantum dots
  • aqueous solution
  • electron transfer
  • photodynamic therapy
  • metal organic framework
  • mass spectrometry
  • crystal structure