Fabio Doctorovich

Fundación Ciencias Exactas y Naturales

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S. Suárez

Adam Mickiewicz University in Poznań

Juan Pellegrino

Fundación Ciencias Exactas y Naturales

Florencia Di Salvo

Fundación Ciencias Exactas y Naturales

Darío A. Estrı́n

University of Buenos Aires

Marcelo A. Martí

Consejo Nacional de Investigaciones Científicas y Técnicas

Damián E. Bikiel

AstraZeneca (United States)

Carina Gaviglio

Comisión Nacional de Energía Atómica

Axel Klein

University of Cologne

Ricardo Baggio

Comisión Nacional de Energía Atómica

Ana Foi

Fundación Ciencias Exactas y Naturales

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Consejo Nacional de Investigaciones Científicas y Técnicas

103

University of Buenos Aires

Fundación Ciencias Exactas y Naturales

Instituto de Química y Fisicoquímica Biológicas

Friedrich-Alexander-Universität Erlangen-Nürnberg

Centre National de la Recherche Scientifique

Universidad Nacional de La Plata

Georgia Institute of Technology

Institute of Inorganic Chemistry of the Slovak Academy of Sciences

University of Stuttgart

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

Inorganic Chemistry (2020)

Nicolás I. Neuman Uta Albold Eleonora Ferretti Shubhadeep Chandra Simon Steinhauer

Two Co(III) complexes (1Py2 and 2Py2) of new corrole ligands H3L1 (5,15-bis(p-methylcarboxyphenyl)-10-(o-methylcarboxyphenyl)corrole) and H3L2 (5,15-bis(p-nitrophenyl)-10-(o-methylcarboxyphenyl)corrole) with two apical pyridine ligands have been synthesized and thoroughly characterized by cyclic voltammetry, UV–vis–NIR, and EPR spectroscopy, spectroelectrochemistry, single-crystal X-ray diffraction studies, and DFT methods. Complexes 1Py2 and 2Py2 possess much lower oxidation potentials than cobalt(III)-tris-pentafluorophenylcorrole (Co(tpfc)) and similar corroles containing pentafluorophenyl (C6F5) substituents, thus allowing access to high oxidation states of the former metallocorroles using mild chemical oxidants. The spectroscopic (UV–vis–NIR and EPR) and electronic properties of several oxidation states of these complexes have been determined by a combination of the mentioned methods. Complexes 1Py2 and 2Py2 undergo three oxidations within 1.3 V vs FcH+/FcH in MeCN, and we show that both complexes catalyze water oxidation in an MeCN/H2O mixture upon the third oxidation, with kobs (TOF) values of 1.86 s–1 at 1.29 V (1Py2) and 1.67 s–1 at 1.37 V (2Py2). These values are five times higher than previously reported TOF values for C6F5-substituted cobalt(III) corroles, a finding we ascribe to the additional charge in the corrole macrocycle due to the increased oxidation state. This work opens up new possibilities in the study of metallocorrole water oxidation catalysts, particularly by allowing spectroscopic probing of high-oxidation states and showing strong substituent-effects on catalytic activity of the corrole complexes.

10.1021/acs.inorgchem.0c02550

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Citations (27)

CCDC 2048374: Experimental Crystal Structure Determination

The Cambridge Structural Database (2023)

Andreas O. Schüren B.M. Ridgway Florencia Di Salvo Luca M. Carella Verena K. Gramm

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

10.5517/ccdc.csd.cc26rhl2

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Halide coordinated homoleptic [Fe₄S₄X₄]²⁻and heteroleptic [Fe₄S₄X₂Y₂]²⁻clusters (X, Y = Cl, Br, I)—alternative preparations, structural analogies and spectroscopic properties in solution and solid state

Dalton Transactions (2015)

Andreas O. Schüren Verena K. Gramm Maximilian Dürr Ana Foi Ivana Ivanović‐Burmazović

New facile methods to prepare iron sulphur halide clusters [Fe4S4X4](2-) from [Fe(CO)5] and elemental sulphur were elaborated. Reactions of ferrous precursors like tetrahalidoferrates(ii) or simple ferrous halides with [Fe(CO)5] and sulphur turned out to be efficient methods to prepare homoleptic [Fe4S4X4](2-) (X = Cl, Br) and heteroleptic clusters [Fe4S4X4-nYn](2-) (X = Cl, Br; Y = Br, I). Solid materials were obtained as salts of BTMA(+) (= benzyltrimethylammonium); the new compounds containing [Fe4S4Br4](2-) and [Fe4S4X2Y2](2-) (X, Y = Cl, Br, I) were all isostructural to (BTMA)2[Fe4S4I4] (monoclinic, Cc) as inferred from synchrotron X-ray powder diffraction. While the solid materials contain defined heteroleptic clusters with a halide X : Y ratio of 2 : 2, dissolving these compounds leads to rapid scrambling of the halide ligands forming mixtures of all five possible [Fe4S4X4-nYn](2-) clusters as could be shown by UHR-ESI MS. The variation of X and Y allowed assignment of the absorption bands in the visible and NIR; the long-wavelength bands around 1100 nm were tentatively assigned to intervalence charge transfer (IVCT) transitions.

Homoleptic

Isostructural

Monoclinic crystal system

10.1039/c5dt02769a

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Tetraaqua(4,4′-dimethyl-2,2′-bipyridine-κ²N,N′)nickel(II) sulfate monohydrate: a simple molecule with an extremely complex hydrogen-bonding scheme

Acta Crystallographica Section C Crystal Structure Communications (2013)

S. Suárez Fabio Doctorovich M.A. Harvey Ricardo Baggio

The title ionic compound, [Ni(C12H12N2)(H2O)4]SO4·H2O, is composed of an Ni(II) cation coordinated by a chelating 4,4'-dimethyl-2,2'-bipyridine ligand via its two N atoms [mean Ni-N = 2.056 (2) Å] and by four aqua ligands [mean Ni-O = 2.073 (9) Å], the net charge being balanced by an external sulfate anion. The whole structure is stabilized by a solvent water molecule. Even though the individual constituents are rather featureless, they generate an extremely complex supramolecular structure consisting of a central hydrogen-bonded two-dimensional hydrophilic nucleus made up of complex cations, sulfate anions and coordinated and solvent water molecules, with pendant hydrophobic 4,4'-dimethyl-2,2'-bipyridine ligands which interact laterally with their neighbours via π-π interactions. The structure is compared with closely related analogues in the literature.

Dimethyl sulfate

2,2'-Bipyridine

Bipyridine

10.1107/s0108270113005088

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Citations (3)

CCDC 946000: Experimental Crystal Structure Determination

The Cambridge Structural Database (2014)

A. Foi Rodrigo S. Corrêa Javier Ellena Fabio Doctorovich Florencia Di Salvo

Crystal (programming language)

10.5517/cc10rd49

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Iridium DMSO driver calculations

Figshare (2017)

B.M. Ridgway Florencia Di Salvo Ana Foi Fabio Doctorovich Rodrigo S. Corrêa

Input and output files and XYZ coordinates from driver calculations on the trans-bis(DMSO)tetrachloroiridate anion. The effect of rotation of one DMSO ligand about the Ir–S axis is investigated by DFT. B3LYP-D def2-svp on all atoms but Ir, which was treated with the Stuttgart-Dresden ECP and def2-tzvp for the valence electrons.

10.6084/m9.figshare.4262423

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Gold and silver anchored cobalt porphyrins used for catalytic water splitting

Materials Chemistry and Physics (2015)

M.A. Morales Vásquez S. Suárez Fabio Doctorovich

10.1016/j.matchemphys.2015.03.065

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Citations (18)

Ammonium 4-methoxybenzenesulfonate

Acta Crystallographica Section E Structure Reports Online (2012)

S. Suárez Fabio Doctorovich Ricardo Baggio

The mol-ecular structure of the title compound, NH(4) (+)·C(7)H(7)O(4)S(-), is featureless [the methoxy C atom deviating 0.173 (6) Å from the phenyl mean plane] with inter-atomic distances and angles in the expected ranges. The main feature of inter-est is the packing mode. Hydro-philic (SO(3) and NH(4)) and hydro-phobic (PhOCH(3)) parts in the structure segregate, the former inter-acting through a dense hydrogen-bonding scheme, leading to a well connected two-dimensional structure parallel to (100) and the latter hydro-phobic groups acting as spacers for an inter-planar separation of c/2 = 10.205 (2) Å. In spite of being aligned along [110], the benzene rings stack in a far from parallel fashion [viz. consecutive ring centers determine a broken line with a 164.72 (12)° zigzag angle], thus preventing any possible π-π inter-action.

Zigzag

10.1107/s1600536812028103

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Molecular Basis for the Electric Field Modulation of Cytochrome c Structure and Function

Journal of the American Chemical Society (2009)

Pablo M. De Biase Damián Álvarez-Paggi Fabio Doctorovich Peter Hildebrandt Darío A. Estrı́n

Cytochrome c (Cyt) is a small soluble heme protein with a hexacoordinated heme and functions as an electron shuttle in the mitochondria and in early events of apoptosis when released to the cytoplasm. Using molecular dynamics simulations, we show here that biologically relevant electric fields induce an increased mobility and structural distortion of key protein segments that leads to the detachment of the sixth axial ligand Met80 from the heme iron. This electric-field-induced conformational transition is energetically and entropically driven and leads to a pentacoordinated high spin heme that is characterized by a drastically lowered reduction potential as well as by an increased peroxidase activity. The simulations provide a detailed atomistic picture of the structural effects of the electric field on the structure of Cyt, which allows a sound interpretation of recent experimental results. The observed conformational change may modulate the electron transfer reactions of Cyt in the mitochondria and, furthermore, may constitute a switch from the redox function in the respiratory chain to the peroxidase function in the early events of apoptosis.

Hemeprotein

10.1021/ja906726n

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Citations (59)

Synthesis, structural elucidation and antiradical activity of a copper (II) naringenin complex

BioMetals (2019)

Gustavo Céliz S. Suárez Analía Natalí Arias José Molina Carlos D. Brondino

10.1007/s10534-019-00187-3

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Citations (25)