Dissection of Light-Induced Charge Accumulation at a Highly Active Iron Porphyrin: Insights in the Photocatalytic CO 2 Reduction.

Iron porphyrins are among the best molecular catalysts for the electrocatalytic CO 2 reduction reaction. Powering these catalysts with the help of photosensitizers comes along with a couple of unsolved challenges that need to be addressed with much vigor. We have designed an iron porphyrin catalyst decorated with urea functions (UrFe) acting as a multipoint hydrogen bonding scaffold towards the CO 2 substrate. We found a spectacular photocatalytic activity reaching unreported TONs and TOFs as high as 7270 and 3720 h -1 , respectively. While the Fe 0 redox state has been widely accepted as the catalytically active species, we show here that the Fe I species is already involved in the CO 2 activation, which represents the rate-determining step in the photocatalytic cycle. The urea functions help to dock the CO 2 upon photocatalysis. DFT calculations bring support to our experimental findings that constitute a new paradigm in the catalytic reduction of CO 2 .