scholarly journals X-ray photoelectron spectra of iron-sulphur proteins

1975 ◽  
Vol 149 (2) ◽  
pp. 471-474 ◽  
Author(s):  
P T Andrews ◽  
C E Johnson ◽  
B Wallbank ◽  
R Cammack ◽  
D O Hall ◽  
...  
Keyword(s):  
Magnetic Susceptibility ◽  
Magnetic State ◽  
High Potential ◽  
Spin Coupling ◽  
Photoelectron Spectra ◽  
Clostridium Pasteurianum ◽  
Active Centre ◽  
Core Polarization ◽  
X Ray ◽  
Polarization Splitting

The X-ray photoelectron spectra of the 2p, 3s and 3p levels of iron in oxidized Clostridium pasteurianum ferredoxin indicate that the eight iron atoms in the molecule are indistinguishable. Their magnetic state is indicated both by core polarization splitting of the 3s electrons, and by ‘shake-up’ satellites on the 2p lines. Similar satellites are observed in the 2p lines of reduced Chromatium high-potential iron-sulphur proteins and oxidized spinach ferredoxin, indicating that there too the iron atoms are magnetic. The low observed magnetic susceptibility of these proteins is therefore due to spin-coupling between the iron atoms in the active centre.

Preparations, Magnetic Susceptibility and Structural Studies of Trinuclear Copper(II) Compounds of 4,4,9,9-Tetramethyl-5,8-diazadodecane-2,11-diol

1988 ◽  
Vol 41 (10) ◽  
pp. 1545 ◽  
Author(s):  
NF Curtis ◽  
GJ Gainsford ◽  
KR Morgan
Keyword(s):  
Magnetic Susceptibility ◽  
Magnetic Moments ◽  
Spin Coupling ◽  
Structural Studies ◽  
Magnetic Susceptibilities ◽  
X Ray ◽  
Square Planar ◽  
Coupling Parameters ◽  
Temperature Ranges ◽  
Oxygen Atoms

Reduction of 4,4,9,9-tetramethyl-5,8-diazadodecane-2,11-dione yields the meso and racemo isomers of 4,4,9,9-tetramethyl-5,8-diazadodecane- 2,11-diol which form trinuclear compounds [Cu3( amat )2](ClO4)2 with all ligand alcohol groups deprotonated . The structure of the compound of the racemo amino alcohol has been determined by X-ray diffractometry [space group, P21/c, a 1594.5(4), b 1786.0(5), c 1419.1(4) pm, β 104.84(2)°, R 0.040, Rw 0.049 for 3466 reflections]. The cation has three copper(II) ions close to colinear (Cu-Cu 294 pm, Cu-Cu-Cu 177°), with the terminal copper(II) ions coordinated by the two nitrogen and two oxygen atoms of the tetradentate diamine-diolato ligand, and the central copper(II) ion by the oxygen atoms of the two ligands . All copper(II) ions have coordination environments intermediate between square planar and tetrahedral, the distortion from square planar being greater for the central ion [angle between planes O2Cu,CuO2 is 45°, compared with 16° between the planes N2Cu,CuO2 of the terminal copper(II) ions]. The magnetic susceptibilities of the compounds, measured over the temperature ranges 96-269 and 99-360 K for the racemo and meso isomers, respectively, are similar. Calculated effective magnetic moments/copper atom range from 1.07 μB at 99 K to 1.28 μB at 360 K. The susceptibility values were fitted to the expression for three spin-coupled copper(II) ions, with resultant spin coupling parameters, J, between adjacent atoms of -212 cm-1 ( meso-amat )and -230 cm-1 (racemo-amat ).

scholarly journals Synthesis and Spectral studies of Ru (II) complexes with Macrocyclic Ligands

2021 ◽  
Vol 37 (4) ◽  
pp. 763-769
Author(s):  
Ashish Rajak ◽  
Arpit Srivastava ◽  
Subhash Chandra Shrivastava ◽  
Ranjeet Singh Chauhan ◽  
Uday Singh Patel ◽  
...  
Keyword(s):  
Magnetic Susceptibility ◽  
Octahedral Geometry ◽  
Molar Conductivity ◽  
Macrocyclic Ligands ◽  
Photoelectron Spectra ◽  
Spectral Studies ◽  
Schiff Base Ligands ◽  
X Ray ◽  
Uv Visible ◽  
Macrocyclic Schiff Base

Fifteen Ru (II) complexes of the type [RuCl2(L)] (where L= N4 donor macrocyclic ligands) have been synthesised by reaction of [(RuCl2(DMSO)4] with fifteen macrocyclic Schiff base ligands containing N4 donors groups. The prepared fifteen [RuCl2(L)] complexes were characterised by elemental analysis, molar conductivity, UV-visible, IR, X- ray photoelectron spectra (XPS) and magnetic susceptibility measurementsand an octahedral geometry was proposed for all these complexes.

The Interplay of Open-Shell Spin-Coupling and Jahn-Teller Distortion in Benzene Radical Cation Probed by X-ray Spectroscopy

2020 ◽  
Author(s):  
Marta L. Vidal ◽  
Michael Epshtein ◽  
Valeriu Scutelnic ◽  
Zheyue Yang ◽  
Tian Xue ◽  
...  
Keyword(s):  
High Harmonic ◽  
Open Shell ◽  
Spin Coupling ◽  
High Symmetry ◽  
Teller Distortion ◽  
Spectral Window ◽  
X Ray ◽  
Jahn Teller ◽  
X Ray Absorption ◽  
Jahn Teller Distortion

We report a theoretical investigation and elucidation of the x-ray absorption spectra of neutral benzene and of the benzene cation. The generation of the cation by multiphoton ultraviolet (UV) ionization as well as the measurement of<br>the carbon K-edge spectra of both species using a table-top high-harmonic generation (HHG) source are described in the companion experimental paper [M. Epshtein et al., J. Phys.<br>Chem. A., submitted. Available on ChemRxiv]. We show that the 1sC -> pi transition serves as a sensitive signature of the transient cation formation, as it occurs outside of the spectral window of the parent neutral species. Moreover, the presence<br>of the unpaired (spectator) electron in the pi-subshell of the cation and the high symmetry of the system result in significant differences relative to neutral benzene in the spectral features associated with the 1sC ->pi* transitions. High-level calculations using equation-of-motion coupled-cluster theory provide the interpretation of the experimental spectra and insight into the electronic structure of benzene and its cation.<br>The prominent split structure of the 1sC -> pi* band of the cation is attributed to the interplay between the coupling of the core -> pi* excitation with the unpaired electron<br>in the pi-subshell and the Jahn-Teller distortion. The calculations attribute most of<br>the splitting (~1-1.2 eV) to the spin coupling, which is visible already at the Franck-Condon structure, and estimate the additional splitting due to structural relaxation to<br>be around ~0.1-0.2 eV. These results suggest that x-ray absorption with increased resolution might be able to disentangle electronic and structural aspects of the Jahn-Teller<br>effect in benzene cation.<br>

scholarly journals Modification of Wood with Monoethanolamino-borate by The Data of X-Ray Photoelectron Spectroscopy

2018 ◽  
Vol 196 ◽  
pp. 04005
Author(s):  
Irina Stepina ◽  
Irina Kotlyarova
Keyword(s):  
Particle Size ◽  
Photoelectron Spectroscopy ◽  
Model Compound ◽  
Hydrolytic Stability ◽  
Photoelectron Spectra ◽  
Wood Cellulose ◽  
Rapid Loss ◽  
X Ray ◽  
Wood Protection ◽  
Cellulose Materials

The difficulty of wood protection from biocorrosion and fire is due to the fact that modifiers in use are washed out from the surface of the substrate under the influence of environmental factors. This results in a rapid loss of the protective effect and other practically important wood characteristics caused by the modification. To solve this problem is the aim of our work. Here, monoethanolaminoborate is used as a modifier, where electron-donating nitrogen atom provides a coordination number equal to four to a boron atom, which determines the hydrolytic stability of the compounds formed. Alpha-cellulose ground mechanically to a particle size of 1 mm at most was used as a model compound for the modification. X-ray photoelectron spectra were recorded on the XSAM-800 spectrometer (Kratos, UK). Prolonged extraction of the modified samples preceded the registration of the photoelectron spectra to exclude the fixation of the modifier molecules unreacted with cellulose. As a result of the experiment, boron and nitrogen atoms were found in the modified substrate, which indicated the hydrolytic stability of the bonds formed between the modifier molecules and the substrate. Therefore monoethanolaminoborate can be considered as a non-extractable modifier for wood-cellulose materials.

scholarly journals Impact of high temperatures on aluminoceladonite studied by Mössbauer, Raman, X-ray diffraction and X-ray photoelectron spectroscopy

2021 ◽  
Author(s):  
Mariola Kądziołka-Gaweł ◽  
Maria Czaja ◽  
Mateusz Dulski ◽  
Tomasz Krzykawski ◽  
Magdalena Szubka
Keyword(s):  
Photoelectron Spectroscopy ◽  
Integral Intensity ◽  
Photoelectron Spectra ◽  
X Ray Diffraction ◽  
Structural Reorganization ◽  
Oh Groups ◽  
X Ray ◽  
Al Content ◽  
Integral Intensity Ratio ◽  
Higher Temperature

AbstractMössbauer, Raman, X-ray diffraction and X-ray photoelectron spectroscopies were used to examine the effects of temperature on the structure of two aluminoceladonite samples. The process of oxidation of Fe2+ to Fe3+ ions started at about 350 °C for the sample richer in Al and at 300 °C for the sample somewhat lower Al-content. Mössbauer results show that this process may be associated with dehydroxylation or even initiate it. The first stage of dehydroxylation takes place at a temperature > 350 °C when the adjacent OH groups are replaced with a single residual oxygen atom. Up to ~500 °C, Fe ions do not migrate from cis-octahedra to trans-octahedra sites, but the coordination number of polyhedra changes from six to five. This temperature can be treated as the second stage of dehydroxylation. The temperature dependence on the integral intensity ratio between bands centered at ~590 and 705 cm−1 (I590/I705) clearly reflects the temperature at which six-coordinated polyhedra are transformed into five-coordinated polyhedra. X-ray photoelectron spectra obtained in the region of the Si2p, Al2p, Fe2p, K2p and O1s core levels, highlighted a route to identify the position of Si, Al, K and Fe cations in a structure of layered silicates with temperature. All the measurements show that the sample with a higher aluminum content and a lower iron content in octahedral sites starts to undergo a structural reorganization at a relatively higher temperature than the less aluminum-rich sample does. This suggests that iron may perform an important role in the initiation of the dehydroxylation of aluminoceladonites.

Cobalt(II) Mercury Tetrathiocyanate Complexes with Lewis Bases

1973 ◽  
Vol 51 (3) ◽  
pp. 438-447 ◽  
Author(s):  
R. Makhija ◽  
L. Pazdernik ◽  
R. Rivest
Keyword(s):  
Magnetic Susceptibility ◽  
Powder Diffraction ◽  
Elemental Analysis ◽  
Far Infrared ◽  
Crystalline Solid ◽  
Ultraviolet Spectroscopy ◽  
X Ray ◽  
Lewis Bases ◽  
Polydentate Ligands

A new series of octahedral cobalt(II) complexes are formed when CoX2(X = Cl, Br, I, SCN) reacts with Hg(SCN)2 in the presence of Lewis bases. These complexes of stoichiometry CoHg(SCN)4•2L (L = THF, dioxane, pyridine, aniline) are pink to violet solids which slowly decompose to the blue crystalline solid, CoHg(SCN)4, the stable magnetic susceptibility standard. On further reaction of CoHg(SCN)4•2THF with mono-, bi-, and polydentate ligands in dry ethanol, complexes of the following types are obtained: CoHg(SCN)4•2L (L = PΦ3), CoHg(SCN)4•2LL (LL = trien), CoHg(SCN)4•3LL (LL = en, bipy), and CoHg(SCN)4•4LL (LL = phen). The stoichiometry of these were determined by elemental analysis. Possible structures of these are discussed with the help of mid and far infrared, visible, and ultraviolet spectroscopy, magnetic susceptibility, and X-ray powder diffraction. Some new i.r. bands like Co—P, Co—N, and Hg—S are assigned in the low region.

Ternary Antimonides RE4T7Sb6 (RE=Gd–Lu; T =Ru, Rh) with Cubic U4Re7Si6-type Structure

2013 ◽  
Vol 68 (9) ◽  
pp. 971-978 ◽  
Author(s):  
Inga Schellenberg ◽  
Ute Ch. Rodewald ◽  
Christian Schwickert ◽  
Matthias Eul ◽  
Rainer Pöttgen
Keyword(s):  
Magnetic Susceptibility ◽  
Single Crystal ◽  
Magnetic Moment ◽  
Induction Furnace ◽  
X Ray Diffraction ◽  
Temperature Dependent ◽  
X Ray ◽  
Antiferromagnetic Ordering ◽  
Arc Melting ◽  
Intermediate Valent

The ternary antimonides RE4T7Sb6 (RE=Gd-Lu; T =Ru, Rh) have been synthesized from the elements by arc-melting and subsequent annealing in an induction furnace. The samples have been characterized by powder X-ray diffraction. Four structures were refined on the basis of single-crystal X-ray diffractometer data: U4Re7Si6 type, space group Im3m with a=862.9(2) pm, wR2=0.0296, 163 F2 values for Er4Ru7Sb6; a=864.1(1) pm, wR2=0.1423, 153 F2 values for Yb4Ru7Sb6; a=872.0(2) pm, wR2=0.0427, 172 F2 values for Tb4Rh7Sb6; and a=868.0(2) pm, wR2=0.0529, 154 F2 values for Er4Rh7Sb6, with 10 variables per refinement. The structures have T1@Sb6 octahedra and slightly distorted RE@T26Sb6 cuboctahedra as building units. The distorted cuboctahedra are condensed via all trapezoidal faces, and this network leaves octahedral voids for the T1 atoms. The ruthenium-based series of compounds was studied by temperature-dependent magnetic susceptibility measurements. Lu4Ru7Sb6 is Pauli-paramagnetic. The antimonides RE4Ru7Sb6 with RE=Dy, Ho, Er, and Tm show Curie-Weiss paramagnetism. Antiferromagnetic ordering occurs at 10.0(5), 5.1(5) and 4.0(5) K for Dy4Ru7Sb6, Ho4Ru7Sb6 and Er4Ru7Sb6, respectively, while Tm4Ru7Sb6 remains paramagnetic. Yb4Ru7Sb6 is an intermediate-valent compound with a reduced magnetic moment of 3.71(1) μB per Yb as compared to 4.54 μB for a free Yb3+ ion

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