El Harakeh Nour, de Morais Ana C P, Rani Neha, Gomez Javier A G, Cousino Abigail, Lanznaster Mauricio, Mazumder Shivnath, Verani Cláudio N
Department of Chemistry, Wayne State University, Detroit, MI, 48202, USA.
Instituto de Química, Universidade Federal Fluminense, 24020-141, Niterói, RJ, Brazil.
Angew Chem Int Ed Engl. 2021 Mar 8;60(11):5723-5728. doi: 10.1002/anie.202013678. Epub 2021 Jan 28.
Two heterometallic photocatalysts were designed and probed for water reduction. Both (bpy) Ru Ni (L ) (1) and (bpy) Ru Ni (L ) Ru (bpy) (2) can generate the low-valent precursor involved in hydride formation prior to dihydrogen generation. However, while the bimetallic [Ru Ni ] (1) requires the presence of an external photosensitizer to trigger catalytic activity, the trimetallic [Ru Ni Ru ] (2) displays significant coupling between the catalytic and light-harvesting units to promote intramolecular multielectron transfer and perform photocatalysis at the Ni center. A concerted experimental and theoretical effort proposes mechanisms to explain why 1 is unable to achieve self-supported catalysis, while 2 is fully photocatalytic.
