Corrole chemistry has witnessed an impressive boost in studies in the last 20 years, thanks to the possibility of preparing corrole derivatives by simple synthetic procedures. The investigation of a large number of corroles has highlighted some peculiar characteristics of these macrocycles, having features different from those of the parent porphyrins. With this progress in the elucidation of corrole properties, attention has been focused on the potential for the exploitation of corrole derivatives in different important application fields. In some areas, the potential of corroles has been studied in certain detail, for example, the use of corrole metal complexes as electrocatalysts for energy conversion. In some other areas, the field is still in its infancy, such as in the exploitation of corroles in solar cells. Herein, we report an overview of the different applications of corroles, focusing on the studies reported in the last five years. 

Corroles at work: a small macrocycle for great applications

Fil: Neuman, Nicolas Ignacio. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Santa Fe. Instituto de Desarrollo Tecnologico para la Industria Quimica. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnologico para la Industria Quimica; Argentina

/pdf/cobalt-corroles-as-electrocatalysts-for-water-oxidation-xz8bd58nr8.pdf

Cobalt Corroles as Electrocatalysts for Water Oxidation: Strong Effect of Substituents on Catalytic Activity

Four A2B type cobalt triaryl corrole complexes (1–4) bearing aldehyde and pyridyl substituents at the 10-meso-phenyl group with different spatial configurations have been synthesized and thoroughly characterized using high-resolution mass spectrometry, nuclear magnetic resonance spectroscopy (NMR), X-ray photoelectron spectroscopy, and single-crystal X-ray diffractometry. These complexes all exhibited good activity in the electrocatalytic hydrogen evolution reaction (HER) when acetic acid, trifluoroacetic acid (TFA) or p-toluenesulfonic acid (TsOH) was used as the proton source. The Tafel catalytic plot revealed the intrinsic characteristics of the catalytic activity. The HER followed the EECEC pathway when acetic acid was used as a proton source, while it proceeded through the EECC or EECEC pathway when using TFA or TsOH as the proton source, depending on the acid concentration. The presence of CoIII–H was detected by 1H NMR, which provided evidence for the catalytic mechanism. The amide pyridyl may function as the proton relay group since the meta-substituted cobalt corroles 3 and 4 exhibited significantly higher turnover frequency (TOF)max values than corroles 1 and 2 in an organic medium.

Synthesis of cobalt A2B triaryl corroles bearing aldehyde and amide pyridyl groups and their performance in electrocatalytic hydrogen evolution

Electrocatalytic hydrogen evolution using triaryl corrole cobalt complex

Electrocatalytic hydrogen evolution of manganese corrole

Pyrene Appended Free-base, Phosphorus(V) and Gallium(III) Corroles and Their β,β′-Linked Corrole Dimers: Synthesis, Photophysical and Electrochemical Properties

First-row transition metal complexes derived from corrole-based ligands are considered efficient catalysts for hydrogen evolution reaction (HER). They are known to enhance the rate of hydrogen production by lowering the energy barrier in the water-splitting process. Here, the synthesis and characterization of a copper corrole complex (CuN2CA) having amine functionality on corrole has been reported. This complex is immobilized onto reduced graphene oxide (CuN2CA-rGO) that exhibited excellent electrocatalytic activity towards hydrogen evolution reaction (HER) with a significantly lower onset potential of -0.57 V vs. NHE efficiency of the corrole complex has significantly been improved when combined with reduced graphene oxide (rGO).

Copper corrole immobilized onto reduced graphene oxide: An efficient electrocatalyst for hydrogen evolution reaction

Catalytic water splitting is a highly promising area of research for the development of a hydrogen-based society. Herein, the synthesis of the bifunctional A2B-type cobalt(III) corrole Co(BAPC)Py2 having the electron-withdrawing meso-pentafluorophenyl and the basic meso-p-aminophenyl substituents is reported. Cyclic voltammetric studies reveal that Co(BAPC)Py2 has two oxidation waves at 0.97 V and 1.42 V associated with the Co(III) → Co(IV) and Co(IV) → Co(V) redox couples, respectively, and two reduction waves at 0.45 and −0.21 V corresponding to the Co(III) → Co(II) and Co(II) → Co(I) redox couples. The as-synthesized Co(BAPC)Py2 corrole has been demonstrated to be an efficient catalyst for the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) in homogeneous (acetonitrile) as well as heterogeneous media. In a homogeneous solution, Co(BAPC)Py2 showed excellent activity towards both the HER, with the first-order rate constant (kcat) of 952.0 s−1, and the OER with the first-order rate constant of 0.2 s−1. The strong electron -withdrawing pentafluorophenyl group present on the corrole ring shifts the redox process towards the anodic direction and facilitates the HER performance, whereas the aminophenyl group increases the basicity of the catalyst that improves the OER activity.

Aminophenyl-substituted cobalt(iii) corrole: a bifunctional electrocatalyst for the oxygen and hydrogen evolution reactions.

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Pyrene Appended Free-base, Phosphorus(V) and Gallium(III) Corroles and Their β,β′-Linked Corrole Dimers: Synthesis, Photophysical and Electrochemical Properties

Copper corrole immobilized onto reduced graphene oxide: An efficient electrocatalyst for hydrogen evolution reaction

Aminophenyl-substituted cobalt(iii) corrole: a bifunctional electrocatalyst for the oxygen and hydrogen evolution reactions.