Corroles and Contracted Porphyrins

Gryko, Daniel T.; Tasior, Mariusz

doi:10.1002/9781119129301.ch7

Cited by 6 publications

(13 citation statements)

References 143 publications

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“…1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 9.28 ppm (2H, d, J = 5.1 Hz), 9.60 (2H, m), 9.71 (4H, m), −2.51 (2H, s). 19 F NMR (377 MHz, CDCl 3 ) δ (ppm): −36.43 (3F, s), and −38.18 (6F, s). Only the pyrrole-H resonance at 9.28 ppm appears as a classical doublet since the three others experience long-range 19 F−H coupling with the meso-CF 3 groups.…”

Section: ■ Conclusionmentioning

confidence: 99%

“…19 F NMR (377 MHz, DMSO-d 6 ) δ (ppm): −36.44 (3F, s), −38.18 (6F, s). Only the pyrrole-H shift resonance at 9.45 ppm appears as a classical doublet since the three others experience long-range 19 F−H coupling with the meso-CF 3 groups. since the three others experience long-range 19 F−H coupling with the meso-CF 3 groups.…”

Section: S Y N T H E S I S O F [ 1 0 1 5 2 0 -T R I S ( T R I Fl U ...mentioning

confidence: 99%

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Surprising Route to a Monoazaporphyrin and Full Characterization of Its Complexes with Five Different 3d Metals

Raslin,

Sercel,

Fridman

et al. 2024

Inorg. Chem.

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In the search for mild agents for the oxidative cyclization of tetrapyrromethane to the corresponding corrole, we discovered a route that leads to a monoazaporphyrin with three meso-CF3 groups. Optimization studies that allowed access to appreciable amounts of this new macrocycle paved the way for the preparation of its cobalt, copper, nickel, zinc, and iron complexes. All complexes were fully characterized by various spectroscopic methods and X-ray crystallography. Their photophysical and electrochemical properties were determined and compared to those of analogous porphyrins in order to deduce the effect of the peripheral N atom. Considering the global efforts for designing efficient alternatives to platinum group metal (PGM) catalysts, they were also absorbed onto a porous carbon electrode material and studied as electrocatalysts for the oxygen reduction reaction (ORR). The cobalt complex was found to be operative at a quite positive catalytic onset potential and with good selectivity for the desirable 4-electrons/4-protons pathway.

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Section: ■ Conclusionmentioning

confidence: 99%

Section: S Y N T H E S I S O F [ 1 0 1 5 2 0 -T R I S ( T R I Fl U ...mentioning

confidence: 99%

Surprising Route to a Monoazaporphyrin and Full Characterization of Its Complexes with Five Different 3d Metals

Raslin,

Sercel,

Fridman

et al. 2024

Inorg. Chem.

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“…The above-described situation improved dramatically in 1999, with the disclosure of the facile one-pot syntheses of 5,10,15-triarylcorroles from pyrrole and aromatic aldehydes. , This signaled a true renaissance, reflected by (a) the introduction of new and improved synthetic methodologies that nowadays allow access to a large variety of aryl-substituted corroles; − (b) large advances in the coordination chemistry of metals chelated by them; − and (c) the introduction of corroles as key elements for practical purposes. , The first two aspects have been summarized in several recent reviews and will hence be only briefly discussed in this Perspective whose focus is on corrole-based applications. But considering that the latter rely mostly on corrole-chelated metal complexes (metallocorroles), some special features must still be mentioned.…”

Section: Introductionmentioning

confidence: 99%

Milestones and Most Recent Advances in Corrole’s Science and Technology

Mahammed

Gross

2023

J. Am. Chem. Soc.

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The renaissance in corrole chemistry is strongly correlated with synthetic breakthroughs that started in 1999, regarding the one-pot rather than multistep syntheses of this heme-like N4 macrocycle. This largely improved synthetic accessibility allowed for technological advances wherein the corresponding metal complexes have since been introduced as key elements. Great emphasis was devoted to the elucidation of the unique fundamental features that distinguish corrole ligands, among them outstanding electron donation (σ by the N atoms and π by the macrocycle) to transition metals chelated by them. Such investigations remain crucial for enabling the by-demand tuning of metallocorrole properties for distinctly different applications. These range from the catalysis of organic reactions, through bioimaging and disease prevention/treatment strategies, to photo- and electrocatalysis for clean energy. Surveyed are the original reports that impacted these developments, together with some of the most recent advances.

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“…The use of aerogels has already proven to significantly increase the active site density of transition metal complexes, which results in some of the state-of-the-art activity in fuel cells . Copper(II) corroles have been known for a long time, and they attract interest also because of their unique electronic configuration. − The FeCu-porphyrrole aerogel in this work was synthesized in an elegant fashion that limited the polymerization reaction to take place solely between the porphyrin and corrole complexes and not between themselves (porphyrin–porphyrin or corrole–corrole), thus bringing the two different complexes and metal centers near each other to mimic the structure of CcO to some extent and form atomically dispersed Fe and Cu sites. This new aerogel architecture was later pyrolyzed in order to increase its electronic conductivity and was thoroughly characterized and studied for the changes that occurred during all synthesis stages and for ORR electrocatalytic activity and fuel cell performance.…”

Section: Introductionmentioning

confidence: 99%

Biomimetic Fe–Cu Porphyrrole Aerogel Electrocatalyst for Oxygen Reduction Reaction

et al. 2023

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The development of bioinspired catalysts for oxygen reduction reaction is one of the most prominent pathways in the search for active materials to replace Pt-based catalysts in fuel cells. Herein, we report innovative bioinspired catalysts using a directed synthetic pathway to create adjacent Cu and Fe sites. This catalyst is composed of a covalent 3D framework in an aerogel form. Aerogels are high surface area and porous hierarchical structures that can allow the formation of ultrahigh active site density and optimized mass transport of reactants and products to and from the catalytic sites. The aerogel-based catalyst exhibits high performance in a half-cell in 0.1 M KOH, with an onset potential of 0.94 V vs RHE and half-wave potential of E 1/2 = 0.80 V vs RHE, high selectivity toward the four-electron reduction of oxygen to hydroxide anions, and high durability. These results are well-translated to the anion exchange membrane fuel cell (AEMFC), reaching an open circuit potential of 0.97 V and iR-corrected peak power density of 0.51 W cm–2. Based on density functional theory calculations, the improved activity relative to the Fe-porphyrin and Cu-corrole is ascribed to the effect of the extended carbon network and the proximity of the metal sites.

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Corroles and Contracted Porphyrins

Cited by 6 publications

References 143 publications

Surprising Route to a Monoazaporphyrin and Full Characterization of Its Complexes with Five Different 3d Metals

Surprising Route to a Monoazaporphyrin and Full Characterization of Its Complexes with Five Different 3d Metals

Milestones and Most Recent Advances in Corrole’s Science and Technology

Biomimetic Fe–Cu Porphyrrole Aerogel Electrocatalyst for Oxygen Reduction Reaction

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