Abstract
Iron hangman porphyrins with phenol, guanidinium, and sulfonic acid proton donor groups placed above the Fe porphyrin platform reduce CO2 to CO with Faradaic efficiencies >93%. Computations show that the activation of CO2 at the Fe center is enhanced by the hanging group. Intramolecular hydrogen bonding from the phenol and guanidinium groups results in a 2.1–6.6 kcal/mol stabilization of CO2 within the hangman pocket; the hanging sulfonate group is deprotonated, thus resulting in destabilization of the CO2 adduct due to unfavorable electrostatic interactions. Electrochemical studies show that Fe hangman porphyrins exhibit canonical S-curve character; together with computation results, the apparent rate constant for CO2 reduction is found to be governed by CO2 binding within the hangman cleft.
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