Unraveling the Oxidation and Spin State of Mn–Corrole through X-ray Spectroscopy and Quantum Chemical Analysis

Paszkiewicz, Mateusz; Biktagirov, Timur; Aldahhak, Hazem; Allegretti, Francesco; Rauls, E.; Schöfberger, Wolfgang; Schmidt, Wolf Gero; Barth, Johannes V.; Gerstmann, Uwe; Klappenberger, Florian

doi:10.1021/acs.jpclett.8b02525

Cited by 17 publications

(15 citation statements)

References 70 publications

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“…The Mn2p scan showed two distinct peaks at 642 eV and 653 eV attributed to 2p 3/2 and 2p 1/2 respectively. The intensity ratio and the position of these two peaks matches well with the Mn III center of previously reported Mn‐corrole . The position of the N1s band at 398.3 eV and the main peak for F1s confirms the integrity of the metal bound corrole species over the carbon paper electrode (Figure S9A).…”

Section: Resultssupporting

confidence: 87%

Electrocatalytic Reduction of CO₂ to Acetic Acid by a Molecular Manganese Corrole Complex

Gonglach

Paul

et al. 2020

Angewandte Chemie

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The controlled electrochemical reduction of carbon dioxide to value added chemicals is an important strategy in terms of renewable energy technologies. Therefore, the development of efficient and stable catalysts in an aqueous environment is of great importance. In this context, we focused on synthesizing and studying a molecular MnIII‐corrole complex, which is modified on the three meso‐positions with polyethylene glycol moieties for direct and selective production of acetic acid from CO2. Electrochemical reduction of MnIII leads to an electroactive MnII species, which binds CO2 and stabilizes the reduced intermediates. This catalyst allows to electrochemically reduce CO2 to acetic acid in a moderate acidic aqueous medium (pH 6) with a selectivity of 63 % and a turn over frequency (TOF) of 8.25 h−1, when immobilized on a carbon paper (CP) electrode. In terms of high selectivity towards acetate, we propose the formation and reduction of an oxalate type intermediate, stabilized at the MnIII‐corrole center.

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Section: Resultssupporting

confidence: 87%

Electrocatalytic Reduction of CO₂ to Acetic Acid by a Molecular Manganese Corrole Complex

Gonglach

Paul

et al. 2020

Angewandte Chemie

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“…Additionally, the stacked conformation has been corroborated for the corrole adsorption onto metallic surfaces such as Au (111), Ag (111), and Pt(111) [76,[87][88][89][90]. Remarkably, the noncovalent adsorption of corroles and corrolato onto Ag (111) displayed adsorption energies in the range of 2.8 -4.7 eV [88].…”

Section: Stability and Structural Properties Of C-g Hybridsmentioning

confidence: 73%

Augmented Magnetic Response and Spin-Transfer in Copper Corrole/Graphene Hybrids - A DFT Study

Wrighton-Araneda

Cortés‐Arriagada

Dreyse

et al. 2022

Preprint

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The search for hybrid materials with outstanding electronic performance is highly demanding Since copper corroles have emerged as versatile building blocks providing outstanding electronic, and reactivity properties, a new series of non-covalent hybrid materials were computationally investigated based on pristine graphene and A3-type copper corrole complexes. The corrole complexes contain strong electron-withdrawing fluorinated substituents at the meso positions. Our results show that the non-innocent character of corrole moiety modulates the structural, electronic, and magnetic properties of the hybrid systems. The graphene-corrole hybrids display outstanding stability via the interplay of dispersion and electrostatic driving forces while graphene act as an electron reservoir for more conductive cases. Furthermore, the hybrid structures display an intriguing magneto-chemical performance since a detailed analysis of magnetic properties evidence how structural and electronic changes contribute to the amplification of the magnetic response also for ferromagnetic and antiferromagnetic cases. This amplification is accompanied by the spin transfer which characterized by a directional spin polarization from the corrole through the graphene surface. Main results suggest that graphene-corrole hybrids are excellent candidates for technologic applications due to the ferromagnetic tendency, the augmented magnetic response, the tunability due to substituents, and the potential conductive properties. Finally, a statistical analysis of magnetic properties suggests correlations between spin transfer, augmented magnetic response, and the geometrical distortion of the copper ligand field, offering exciting hints about how to modulate the magnetic response in the studied hybrid systems.

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“…The XPS spectra were calculated using a ΔSCF approach, which, for light elements such as nitrogen, has been shown to give highly accurate core-level shifts (CLS). 58 − 61 To model the 1s (2p) core holes of the C and N (Zn) species, multiprojector (gauge including (GI-))projector augmented wave (PAW) pseudopotentials 62 with a corresponding occupation of the inner shells were generated. The resulting core-level shifts (CLS) were superimposed and convoluted by assuming a linewidth of 0.7 eV.…”

Section: Materials and Methodsmentioning

confidence: 99%

Toward Efficient Toxic-Gas Detectors: Exploring Molecular Interactions of Sarin and Dimethyl Methylphosphonate with Metal-Centered Phthalocyanine Structures

et al. 2020

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The rapid and reliable detection of lethal agents such as sarin is of increasing importance. Here, density-functional theory (DFT) is used to compare the interaction of sarin with single-metal-centered phthalocyanine (MPc) and MPc layer structures to a benign model system, i.e., the adsorption of dimethyl methylphosphonate (DMMP). The calculations show that sarin and DMMP behave nearly identical to the various MPcs studied. Among NiPc, CuPc, CoPc, and zinc phthalocyanine (ZnPc), we find the interaction of both sarin and DMMP to be the strongest with ZnPc, both in terms of interaction energy and adsorption-induced work function changes. ZnPc is thus proposed as a promising sensor for sarin detection. Using X-ray photoelectron spectroscopy, the theoretically predicted charge transfer from DMMP to ZnPc is confirmed and identified as a key component in the sensing mechanism.

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Unraveling the Oxidation and Spin State of Mn–Corrole through X-ray Spectroscopy and Quantum Chemical Analysis

Cited by 17 publications

References 70 publications

Electrocatalytic Reduction of CO₂ to Acetic Acid by a Molecular Manganese Corrole Complex

Electrocatalytic Reduction of CO₂ to Acetic Acid by a Molecular Manganese Corrole Complex

Augmented Magnetic Response and Spin-Transfer in Copper Corrole/Graphene Hybrids - A DFT Study

Toward Efficient Toxic-Gas Detectors: Exploring Molecular Interactions of Sarin and Dimethyl Methylphosphonate with Metal-Centered Phthalocyanine Structures

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Unraveling the Oxidation and Spin State of Mn–Corrole through X-ray Spectroscopy and Quantum Chemical Analysis

Cited by 17 publications

References 70 publications

Electrocatalytic Reduction of CO2 to Acetic Acid by a Molecular Manganese Corrole Complex

Electrocatalytic Reduction of CO2 to Acetic Acid by a Molecular Manganese Corrole Complex

Augmented Magnetic Response and Spin-Transfer in Copper Corrole/Graphene Hybrids - A DFT Study

Toward Efficient Toxic-Gas Detectors: Exploring Molecular Interactions of Sarin and Dimethyl Methylphosphonate with Metal-Centered Phthalocyanine Structures

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Electrocatalytic Reduction of CO₂ to Acetic Acid by a Molecular Manganese Corrole Complex

Electrocatalytic Reduction of CO₂ to Acetic Acid by a Molecular Manganese Corrole Complex