Oxygen Binding to Cobalt and Iron Phthalocyanines As Determined from in Situ X-ray Absorption Spectroscopy

Miedema, Piter S.; Schooneveld, Matti M. van; Bogerd, René; Rocha, Túlio C. R.; Hävecker, Michael; Knop‐Gericke, Axel; Groot, Frank M. F. de

doi:10.1021/jp209295f

Cited by 48 publications

(48 citation statements)

References 49 publications

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“…Another interesting observation they make is that the shake-up of 2p 1/2 is at 4.6 eV, which is still a little bit higher than the shake-up of 1s photoemission. This would imply that the 2p 1/2 3d electron interaction is already much weaker than 2p 3/2 3d, an observation which fits well to features obtained in the L 3 versus L 2 edge of X-ray absorption [5,6,25].…”

Section: Resultssupporting

confidence: 76%

“…In particular for 3d transition metal (TMs) elements the common choice for photoemission studies concern mostly the 2p and 3s core level spectra, whose binding energies are in between 400 and 1000 eV, are easily accessible by employing quasi-monochromatic radiation provided by X-ray laboratory (Mg K␣ and Al K␣ at 1253.4 eV and 1486.3 eV, respectively) or synchrotron radiation sources to access the whole soft X-ray range. The 2p or 3s core level wavefunction overlaps strongly with the 3d states and make these 2p and 3s spectra sensitive to the electronic and magnetic structure of the probed elements [2] and in many cases the interpretation of the spectra has been well-established using the charge transfer multiplet model [3][4][5][6].…”

Section: Introductionmentioning

confidence: 99%

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Iron 1s X-ray photoemission of Fe2O3

Miedema

Borgatti

Offi

et al. 2015

Journal of Electron Spectroscopy and Related Phenomena

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We present the 1s X-ray photoemission spectrum of α-Fe2O3 in comparison with its 2p photoemission spectrum. We show that in case of transition metal oxides, because the 1s core hole is not affected by core hole spin-orbit coupling and almost not affected by core-valence multiplet effects, the Fe 1s spectrum and the complementary charge transfer multiplet calculations allow for an accurate determination of the charge transfer parameters. The consistency of the obtained parameters for the 1s photoemission was confirmed with 2p photoemission calculations and compared to 2p experimental photoemission spectra

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Section: Resultssupporting

confidence: 76%

Section: Introductionmentioning

confidence: 99%

Iron 1s X-ray photoemission of Fe2O3

Miedema

Borgatti

Offi

et al. 2015

Journal of Electron Spectroscopy and Related Phenomena

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“…These plots show the (a) d z 2 in good agreement with the previous crystallographic results about O 2 adduction on these metal complexes. 44 We chose the O 2 -CoPcF 16 adsorption system as a representative case to illustrate the bond formation in an end-on O 2 adsorption configuration. In Fig.…”

Section: Electronic Structure Of O 2 Adsorption On Tm-n 4 Macrocycmentioning

confidence: 99%

Correlation between oxygen adsorption energy and electronic structure of transition metal macrocyclic complexes

Liu

Lei

Wang

2013

The Journal of Chemical Physics

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Oxygen adsorption energy is directly relevant to the catalytic activity of electrocatalysts for oxygen reduction reaction (ORR). In this study, we established the correlation between the O2 adsorption energy and the electronic structure of transition metal macrocyclic complexes which exhibit activity for ORR. To this end, we have predicted the molecular and electronic structures of a series of transition metal macrocyclic complexes with planar N4 chelation, as well as the molecular and electronic structures for the O2 adsorption on these macrocyclic molecules, using the density functional theory calculation method. We found that the calculated adsorption energy of O2 on the transition metal macrocyclic complexes was linearly related to the average position (relative to the lowest unoccupied molecular orbital of the macrocyclic complexes) of the non-bonding d orbitals (d(z(2)), d(xy), d(xz), and d(yz)) which belong to the central transition metal atom. Importantly, our results suggest that varying the energy level of the non-bonding d orbitals through changing the central transition metal atom and/or peripheral ligand groups could be an effective way to tuning their O2 adsorption energy for enhancing the ORR activity of transition metal macrocyclic complex catalysts.

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“…[1][2][3][4][5] Their electronic and magnetic properties are critically dominated by the electronic configuration of the transition-metal ions and their local environments, especially the ground state and the first-excited state. In planar MPc's the metal center is surrounded by the four pyrrolic nitrogen atoms of the macrocycle in an environment of D 4h symmetry, resulting in a splitting of the transition-metal 3d levels into four states and the physical relevant irreducible representations of this group are a 1g (d 3z 2 −r 2), b 1g (d x 2 −y 2), e g (d xz , d yz ) and b 2g (d xy ).…”

Section: Introductionmentioning

confidence: 99%

The significant role of covalency in determining the ground state of cobalt phthalocyanines molecule

Zhou

Zhang

et al. 2016

AIP Advances

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To shed some light on the metal 3d ground state configuration of cobalt phthalocyanines system, so far in debate, we present an investigation by X-ray absorption spectroscopy (XAS) at Co L2,3 edge and theoretical calculation. The density functional theory calculations reveal highly anisotropic covalent bond between central cobalt ion and nitrogen ligands, with the dominant σ donor accompanied by weak π-back acceptor interaction. Our combined experimental and theoretical study on the Co-L2,3 XAS spectra demonstrate a robust ground state of 2A1g symmetry that is built from 73% 3d7 character and 27% 3d8L¯ (L¯ denotes a ligand hole) components, as the first excited-state with 2Eg symmetry lies about 158 meV higher in energy. The effect of anisotropic and isotropic covalency on the ground state was also calculated and the results indicate that the ground state with 2A1g symmetry is robust in a large range of anisotropic covalent strength while a transition of ground state from 2A1g to 2Eg configuration when isotropic covalent strength increases to a certain extent. Here, we address a significant anisotropic covalent effect of short Co(II)-N bond on the ground state and suggest that it should be taken into account in determining the ground state of analogous cobalt complexes.

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Oxygen Binding to Cobalt and Iron Phthalocyanines As Determined from in Situ X-ray Absorption Spectroscopy

Cited by 48 publications

References 49 publications

Iron 1s X-ray photoemission of Fe2O3

Iron 1s X-ray photoemission of Fe2O3

Correlation between oxygen adsorption energy and electronic structure of transition metal macrocyclic complexes

The significant role of covalency in determining the ground state of cobalt phthalocyanines molecule

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