Double Hangman Iron Porphyrin and the Effect of Electrostatic Nonbonding Interactions on Carbon Dioxide Reduction.,The Journal of Physical Chemistry Letters

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Double Hangman Iron Porphyrin and the Effect of Electrostatic Nonbonding Interactions on Carbon Dioxide Reduction.
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2020-02-05 , DOI: 10.1021/acs.jpclett.9b03897
Charles G Margarit ₁ , Naomi G Asimow ₁ , Miguel I Gonzalez ₁ , Daniel G Nocera ₁

Affiliation

Hangman porphyrins influence the reaction rates of small molecule activation by positioning a functional group in the secondary coordination sphere of the metal center. Electrocatalysis by hangman porphyrins has examined only one face modification of the macrocycle with a hanging group, thus allowing for circumvention of secondary sphere effects by reaction of the small molecule on the opposite face of the hangman cleft. We now report the synthesis and characterization of a double hangman Fe porphyrin in which both faces of the macrocycle are modified with a hanging group. With this double hangman architecture, we are able to unequivocally examine the role of electrostatic interactions on the carbon dioxide reduction reaction (CO2RR) and show that CO2RR rates are significantly attenuated, consistent with the initial reduction of CO2 to generate the anion, whose binding is diminished within the negatively charged carboxylic groups of the hangman cleft. The results demonstrate the pronounced role that nonbonding electrostatic interactions may play in CO2RR and highlight the need to manage deleterious electrostatic interactions during catalytic turnover.

中文翻译：

双Hangman铁卟啉和静电非键相互作用对二氧化碳还原的影响。

man子手卟啉通过将官能团放置在金属中心的二级配位区内来影响小分子活化的反应速率。子手卟啉的电催化仅检查了带有悬挂基团的大环的一个表面修饰，因此可以通过by子手裂口相反面上的小分子反应来规避次级球效应。现在，我们报告双子手铁卟啉的合成和表征，其中大环的两个面都用一个悬挂基团修饰。借助这种双绞机架构，我们可以明确检查静电相互作用对二氧化碳还原反应（CO2RR）的作用，并表明CO2RR速率显着降低，这与最初产生的CO2减少相一致，从而产生了阴离子，该阴离子的结合在子手裂隙的带负电荷的羧基内减弱了。结果表明，非键合静电相互作用可能在CO2RR中发挥重要作用，并强调了在催化转化过程中需要管理有害的静电相互作用。

更新日期：2020-02-24

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