Study of metallocorrole water oxidation catalysts by spectroscopic, electrochemical and computational methods.

NICOLÁS I. NEUMAN

Chemnitz

Encuentro; 11th Central European Meeting on Molecular Electrochemistry CEMME 2019; 2019

Technische Universitat Chemnitz

Corrolesare porphyrinoid macrocycles capable of stabilizing metals in highformal oxidation states, giving complexes with rich chemical,spectroscopic and redox properties.1Amongst other reactions, metallocorroles have been used as H2and O2evolution2,3and CO2and O2reduction4catalysts. Many water oxidation studies were performed using cobaltcorroles with highly electron withdrawing (EW) pentafluorophenylsubstituents,3which make achieving high oxidation states more difficult. In thiswork we focused on cobalt corroles with strong (nitro) andintermediate (methylester) EW groups, which in turn can be convertedto water soluble amino or carboxylate substituents. We synthesized,characterized and studied the redox and spectroscopic properties oftwo cobalt corroles (Figure 1) using UV-visible-NIR and EPRspectroscopy and spectroelectrochemistry, cyclic voltammetry anddensity functional theory computations, and explored their potentialactivity in water oxidation electrocatalysis. We particularly focusedon establishing the spectroscopic features of the differentaccessible oxidation states of each corrole, with the aim ofproviding a firm standing ground for future studies of more reactiveintermediates in the catalytic cycle.p { direction: ltr; color: #000000; orphans: 0; widows: 0; background: transparent }p.western { font-family: "Times New Roman", serif; font-size: 12pt; so-language: cs-CZ }p.cjk { font-family: "Times New Roman", serif; font-size: 12pt }p.ctl { font-family: "Times New Roman", serif; font-size: 12pt; so-language: ar-SA }a:link { color: #0563c1; text-decoration: underline }