X-ray photoelectron spectra of heterometallic 3d-metal carboxylate complexes

The electronic structure and magnetic states in the heterometallic hexanuclear complex Mn 4 II Fe 2 III (μ4-O)2(Piv)10 • MeCN4 have been studied by X-ray photoelectron spectroscopy (XPS). The substitution of two Mn atoms for two Fe atoms in the hexanuclear complex was found to have an effect on the patterns of iron and manganese X-ray photoelectron spectra. XPS data are evidence of the high-spin paramagnetic state of MnII and FeIII atoms, as well as of the ligand-metal charge transfer upon complex formation. In the heteroatomic complex, the degree of bond covalence increased for both the manganese and iron atoms. The results obtained are in good agreement with X-ray diffraction data. © 2011 Pleiades Publishing, Ltd

X-ray photoelectron spectra of heterometallic 3d-metal carboxylate complexes

The electronic structure and magnetic states in the heterometallic hexanuclear complex Mn 4 II Fe 2 III (μ4-O)2(Piv)10 • MeCN4 have been studied by X-ray photoelectron spectroscopy (XPS). The substitution of two Mn atoms for two Fe atoms in the hexanuclear complex was found to have an effect on the patterns of iron and manganese X-ray photoelectron spectra. XPS data are evidence of the high-spin paramagnetic state of MnII and FeIII atoms, as well as of the ligand-metal charge transfer upon complex formation. In the heteroatomic complex, the degree of bond covalence increased for both the manganese and iron atoms. The results obtained are in good agreement with X-ray diffraction data. © 2011 Pleiades Publishing, Ltd

XPS study of the electronic structure of heterometallic complexes Fe 2MO(Piv)6(HPiv)3 (M = Ni, Co)

Heterometallic complexes Fe2MO(Piv)6(HPiv) 3 (M = Ni, Co) have been studied by XPS. The complexes are identified as high-spin complexes with metal atoms in oxidation states M(II) and M(III). A change in the ligand environment of metal atoms has an effect on both the energetic state of metal atoms and the XPS pattern. The substitution of a Co atom for the nickel atom in the heterometallic complexes changes the XPS pattern of iron and their magnetic state. For the Fe2MO(Piv) 6(HPiv)3 complexes, quantum-chemical calculations have been performed at the density functional theory (DFT) level. In combination with XPS and magnetochemistry data, the quantum-chemical calculation demonstrates that the Fe, Ni, and Co atoms in the trinuclear complexes are in the high-spin local state and that the ground state is dominated by antiferromagnetic exchange interaction. © 2013 Pleiades Publishing, Ltd

X-ray photoelectron Fe3s and Fe3p spectra of polynuclear trimethylacetate iron complexes

X-ray photoelectron Fe3s and Fe3p spectra are employed to study the electron structure and the spin magnetic state of bi-, tri-, and hexa-nuclear trimethylacetate iron complexes. Assignment of the spectra is performed based on an isolated-ion Pauli-Fock calculation of Fe3s and Fe3p spectra of the Fe atoms in bi-and tri-valent states. Nonequivalent FeIII and FeII atoms are detected in tri-and hexa-nuclear complexes. Paramagnetic-limit molecular magnetic moments are calculated using effective atomic magnetic moments obtained from spin-sensitive spectral characteristics. Comparison of those values with the magnetic measurements data demonstrates antiferromagnetic interaction within the complexes. © 2010 Elsevier B.V. All rights reserved

X-ray photoelectron Fe3s and Fe3p spectra of polynuclear trimethylacetate iron complexes

X-ray photoelectron Fe3s and Fe3p spectra are employed to study the electron structure and the spin magnetic state of bi-, tri-, and hexa-nuclear trimethylacetate iron complexes. Assignment of the spectra is performed based on an isolated-ion Pauli-Fock calculation of Fe3s and Fe3p spectra of the Fe atoms in bi-and tri-valent states. Nonequivalent FeIII and FeII atoms are detected in tri-and hexa-nuclear complexes. Paramagnetic-limit molecular magnetic moments are calculated using effective atomic magnetic moments obtained from spin-sensitive spectral characteristics. Comparison of those values with the magnetic measurements data demonstrates antiferromagnetic interaction within the complexes. © 2010 Elsevier B.V. All rights reserved

XPs study of the electronic structure of binuclear 3d transition metal pivalate complexes

Binuclear pivalate complexes of 3d transition metals (manganese, iron, cobalt, and nickel) with the same ligand environment and a lantern structure have been studied by X-ray photoelectron spectroscopy. The M2p, M3s, C1s, O1s, and N1s X-ray photoelectron spectra have been examined. A redistribution of elec- tron density in the OCO group has been revealed. It has been shown that the theory fits the experimental data on the energy separation between the high- and low-spin components in the M3s spectra and between the spin doublet components in the M2p spectra. It has been demonstrated that the iron, cobalt, and nickel com- plexes are paramagnetic at room temperature, whereas the manganese complex exhibits antiferromagnetic properties. There is a correlation between the size of the 3d subshell of the transition metal atom and the M- O and M-N bond lengths. © Pleiades Publishing, Ltd., 2012

XPS study of the electronic structure of heterometallic complexes Fe 2MO(Piv)6(HPiv)3 (M = Ni, Co)

Heterometallic complexes Fe2MO(Piv)6(HPiv) 3 (M = Ni, Co) have been studied by XPS. The complexes are identified as high-spin complexes with metal atoms in oxidation states M(II) and M(III). A change in the ligand environment of metal atoms has an effect on both the energetic state of metal atoms and the XPS pattern. The substitution of a Co atom for the nickel atom in the heterometallic complexes changes the XPS pattern of iron and their magnetic state. For the Fe2MO(Piv) 6(HPiv)3 complexes, quantum-chemical calculations have been performed at the density functional theory (DFT) level. In combination with XPS and magnetochemistry data, the quantum-chemical calculation demonstrates that the Fe, Ni, and Co atoms in the trinuclear complexes are in the high-spin local state and that the ground state is dominated by antiferromagnetic exchange interaction. © 2013 Pleiades Publishing, Ltd