1. Long-range electrostatic effects from intramolecular Lewis acid binding influence the redox properties of cobalt-porphyrin complexes.
- Author
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Alvarez-Hernandez JL, Zhang X, Cui K, Deziel AP, Hammes-Schiffer S, Hazari N, Piekut N, and Zhong M
- Abstract
A Co
II -porphyrin complex (1) with an appended aza-crown ether for Lewis acid (LA) binding was synthesized and characterized. NMR spectroscopy and electrochemistry show that cationic group I and II LAs ( i.e. , Li+ , Na+ , K+ , Ca2+ , Sr2+ , and Ba2+ ) bind to the aza-crown ether group of 1. The binding constant for Li+ is comparable to that observed for a free aza-crown ether. LA binding causes an anodic shift in the CoII /CoI couple of between 10 and 40 mV and also impacts the CoIII /CoII couple. The magnitude of the anodic shift of the CoII /CoI couple varies linearly with the strength of the LA as determined by the p Ka of the corresponding metal-aqua complex, with dications giving larger shifts than monocations. The extent of the anodic shift of the CoII /CoI couple also increases as the ionic strength of the solution decreases. This is consistent with electric field effects being responsible for the changes in the redox properties of 1 upon LA binding and provides a novel method to tune the reduction potential. Density functional theory calculations indicate that the bound LA is 5.6 to 6.8 Å away from the CoII ion, demonstrating that long-range electrostatic effects, which do not involve changes to the primary coordination sphere, are responsible for the variations in redox chemistry. Compound 1 was investigated as a CO2 reduction electrocatalyst and shows high activity but rapid decomposition., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)- Published
- 2024
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