scholarly journals A complete biomimetic iron-sulfur cubane redox series

2021 ◽  
Author(s):  
Liam Grunwald ◽  
Martin Clémancey ◽  
Daniel Klose ◽  
Lionel Dubois ◽  
Serge Gambarelli ◽  
...  
Keyword(s):  
Ground State ◽  
Variable Temperature ◽  
Oxidation States ◽  
Alkali Metal Cations ◽  
X Ray Diffraction ◽  
X Ray ◽  
Iron Sulfur ◽  
Mössbauer Isomer Shift ◽  
Complete Series ◽  
Electronic Ground

Synthetic iron-sulfur cubanes are essential models for biological cofactors in the more complex enzymatic environments. However, a complete series of [Fe4S4]n complexes spanning all biorelevant oxidation states (n = 0-3+) has never been prepared. Here, we demonstrate that the use of a bulky arylthiolate ligand promoting the encapsulation of alkali-metal cations in the vicinity of the cubane enables the synthesis of such a series. Characterization by EPR, 57Fe Mössbauer spectroscopy, UV-Vis electronic absorption and variable-temperature X-ray diffraction analysis reveals key trends for the Fe4S4 core’s geometry as well as for the Mössbauer isomer shift, which both correlate systematically with oxidation state. Furthermore, we confirm the S=4 electronic ground state of the most reduced member, [Fe4S4]0, in agreement with that proposed for the all-ferrous cubanes in Nature.

scholarly journals A complete biomimetic iron-sulfur cubane redox series

2021 ◽  
Author(s):  
Liam Grunwald ◽  
Martin Clémancey ◽  
Daniel Klose ◽  
Lionel Dubois ◽  
Serge Gambarelli ◽  
...  
Keyword(s):  
Ground State ◽  
Variable Temperature ◽  
Oxidation States ◽  
Alkali Metal Cations ◽  
X Ray Diffraction ◽  
X Ray ◽  
Iron Sulfur ◽  
Mössbauer Isomer Shift ◽  
Complete Series ◽  
Electronic Ground

Synthetic iron-sulfur cubanes are essential models for biological cofactors in the more complex enzymatic environments. However, a complete series of [Fe4S4]n complexes spanning all biorelevant oxidation states (n = 0-3+) has never been prepared. Here, we demonstrate that the use of a bulky arylthiolate ligand promoting the encapsulation of alkali-metal cations in the vicinity of the cubane enables the synthesis of such a series. Characterization by EPR, 57Fe Mössbauer spectroscopy, UV-Vis electronic absorption and variable-temperature X-ray diffraction analysis reveals key trends for the Fe4S4 core’s geometry as well as for the Mössbauer isomer shift, which both correlate systematically with oxidation state. Furthermore, we confirm the S=4 electronic ground state of the most reduced member, [Fe4S4]0, in agreement with that proposed for the all-ferrous cubanes in Nature.

Polynuclear Gold Complexes of the Carbodiimide Unit [N=C=N]2-

1996 ◽  
Vol 51 (6) ◽  
pp. 801-805 ◽  
Author(s):  
W. Schneider ◽  
K. Angermaier ◽  
H. Schmidbaur
Keyword(s):  
Low Temperature ◽  
Ground State ◽  
Variable Temperature ◽  
Trinuclear Complex ◽  
X Ray Diffraction ◽  
X Ray ◽  
Nmr Data ◽  
Site Exchange ◽  
High Yields ◽  
State Configuration

Abstract The reaction of N,N′-bis(trimethylsilyl)carbodiimide with equimolar quantities of tris[(triphenylphosphine)gold]oxonium tetrafluoroborate in dichloromethane at -40°C gives high yields of a trinuclear complex {[(Ph3P)Au]2NCN[Au(PPh3)]}+ BF4-(1). According to variable temperature NMR data the cation is fluxional in solution with a rapid site exchange of the [(Ph3P)Au] units, but has an unsymmetrical (N,N,N′) low temperature ground state configuration. A single crystal X-ray diffraction study has shown that in the crystal lattice these cations are associated further into cyclic, hexanuclear dimers through two short head-to-tail Au-Au contacts (auriophilicity). Treatment of complex 1 with one equivalent of [(Ph3P)Au]+ BF4- in tetrahydrofuran affords a tetranuclear complex {[(Ph3P)Au]2NCN[Au(PPh3)]2}2+ 2BF4- (2). The ambient temperature NMR spectra of 2 suggest a fluxional, pseudo-symmetrical structure, but at low temperature a set of three 31P signals (1:2:3 intensity) indicates an aggregation into higher nuclearity species with non-equivalent [Au(PPh3)] units

X-ray diffraction study of the electronic ground state of (meso-tetraphenylporphinato)iron(II)

1990 ◽  
Vol 112 (20) ◽  
pp. 7294-7298 ◽  
Author(s):  
Naiyin Li ◽  
Zhengwei Su ◽  
Philip Coppens ◽  
John Landrum
Keyword(s):  
Diffraction Study ◽  
Ground State ◽  
Electronic Ground State ◽  
X Ray Diffraction ◽  
X Ray ◽  
Electronic Ground

scholarly journals Born out of Fire and Ice: Polymorph Studies of the Antiviral Famciclovir

Crystals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 129
Author(s):  
Liana Vella-Zarb ◽  
Ulrich Baisch
Keyword(s):  
Variable Temperature ◽  
Chemical Properties ◽  
Crystal Form ◽  
X Ray Diffraction ◽  
Crystal Forms ◽  
X Ray ◽  
Physical Chemical ◽  
Diffraction Patterns ◽  
Crystalline Forms

There is much interest and focus on solid forms of famciclovir. However, in spite of the abundance of reported differences in oral bioavailability, compressibility, and other physical–chemical properties of the various crystal forms of this drug, very little precise structural analysis is available in the literature to date. The form used in the commercial formulation is the anhydrous form I. Patents and patent applications report three different anhydrous crystalline forms on the basis of unindexed powder diffraction patterns. Single-crystal and variable-temperature X-ray diffraction experiments using the commercially available anhydrous form of famciclovir were carried out and led not only to the crystal structure determination of the anhydrous form I, but also to discovery of a new crystal form of anhydrous famciclovir from powder data.

scholarly journals Investigation of Solvatomorphism and Its Photophysical Implications for Archetypal Trinuclear Au3(1-Methylimidazolate)3

Molecules ◽  
2021 ◽  
Vol 26 (15) ◽  
pp. 4404
Author(s):  
Shengyang Guan ◽  
David C. Mayer ◽  
Christian Jandl ◽  
Sebastian J. Weishäupl ◽  
Angela Casini ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Density Functional ◽  
Bulk Material ◽  
Variable Temperature ◽  
Active Phase ◽  
Solvent Free ◽  
X Ray Diffraction ◽  
X Ray ◽  
Aurophilic Interactions

A new solvatomorph of [Au3(1-Methylimidazolate)3] (Au3(MeIm)3)—the simplest congener of imidazolate-based Au(I) cyclic trinuclear complexes (CTCs)—has been identified and structurally characterized. Single-crystal X-ray diffraction revealed a dichloromethane solvate exhibiting remarkably short intermolecular Au⋯Au distances (3.2190(7) Å). This goes along with a dimer formation in the solid state, which is not observed in a previously reported solvent-free crystal structure. Hirshfeld analysis, in combination with density functional theory (DFT) calculations, indicates that the dimerization is generally driven by attractive aurophilic interactions, which are commonly associated with the luminescence properties of CTCs. Since Au3(MeIm)3 has previously been reported to be emissive in the solid-state, we conducted a thorough photophysical study combined with phase analysis by means of powder X-ray diffraction (PXRD), to correctly attribute the photophysically active phase of the bulk material. Interestingly, all investigated powder samples accessed via different preparation methods can be assigned to the pristine solvent-free crystal structure, showing no aurophilic interactions. Finally, the observed strong thermochromism of the solid-state material was investigated by means of variable-temperature PXRD, ruling out a significant phase transition being responsible for the drastic change of the emission properties (hypsochromic shift from 710 nm to 510 nm) when lowering the temperature down to 77 K.

Reactions of (η5-C9H7)Rh(η2-C2H4)2 with quinones: molecular structure of [(η5-C9H7)Rh(2,3,5,6-C6O2(CH3)4)]

1999 ◽  
Vol 77 (2) ◽  
pp. 199-204
Author(s):  
Stephen A Westcott ◽  
Nicholas J Taylor ◽  
Todd B Marder
Keyword(s):  
Molecular Structure ◽  
Least Squares ◽  
Ground State ◽  
Slip Parameter ◽  
X Ray Diffraction ◽  
X Ray ◽  
A Value ◽  
Hinge Angle

Reactions of (η5-C9H7)Rh(η2-C2H4)2 (1) with quinones were investigated. Substitution of the labile ethylene ligands was observed upon addition of either duroquinone (2,3,5,6-tetramethyl-1,4-benzoquinone) or 1,4-benzoquinone to complex 1. The molecular structure of neutral (η5-C9H7)Rh(2,3,5,6-C6O2(CH3)4) (3), determined by X-ray diffraction, shows that the duroquinone ligand lies in a plane nearly parallel to the indenyl group. The carbonyl moieties of duroquinone lie in a plane incorporating Rh, C2, and the midpoint between C3a and C7a of the indenyl ring. The slip parameter (Δ= d(average Rh-C3a,7a) -d(average Rh-C1,3)) was calculated to be 0.112(2) Å; whereas a value of ca. 0.05 Å had been obtained previously from film data. Values for the hinge angle (HA = angle between normals to the least-squares planes defined by C1, C2, C3 and C1, C7a, C3a, C3) and fold angle (FA = angle between normals to the least-squares planes defined by C1, C2, C3 and C3a, C4, C5, C7, C7a) are 7.2° and 4.0°, respectively.Key words: indenyl, rhodium, quinones, ring-slippage, ground-state distortion.

Comparative Spectroscopic Studies on Luminescence Performance of Er3+ Doped Tellurite Glass Embedded with Different Nanoparticles (Ag Co and Fe) at 0.55 μm Emission

2021 ◽  
Vol 317 ◽  
pp. 81-86
Author(s):  
Syariffah Nurathirah Syed Yaacob ◽  
Md. Rahim Sahar ◽  
Faizani Mohd Noor ◽  
Nur Liyana Amiar Rodin ◽  
Siti Khadijah Mohd Zain ◽  
...  
Keyword(s):  
Energy Transfer ◽  
Ground State ◽  
Tellurite Glass ◽  
Spectroscopic Studies ◽  
The Other ◽  
X Ray Diffraction ◽  
Melt Quenching ◽  
X Ray ◽  
Doped Glass ◽  
Luminescence Performance

The spectroscopic performance of Er3+ doped glass at 0.55 mm emission contain different nanoparticles NPs have been comparatively evaluated. Glass containing 1.0 mol % of Er3+ doped with different NPs (Ag, Co and Fe ) have been prepared using melt quenching technique. X-ray diffraction analysis reveals the all the prepared samples are amorphous. The UV-Vis absorption spectra of all glasses show several prominent peaks at 525 nm, 660 nm, 801nm, 982 nm and 959 nm due to transition from ground state 4I15/2 to different excited of 2H11/2, 4F9/2, 4I9/2, 4I11/2, and 4I13/2. The emission of Er3+ at 0.55 mm for glass contain Ag NP shows significant enhancement about 3 folds up to 0.6 mol%. On the other hand, the emission of Er3+ at 0.55 mm for glass containing Fe NPs and Co NPs intensely quench probably due to the energy-transfer from Er3+ ion to NPs and magnetic contributions.

W-Doped VO2 (M) with Tunable Phase Transition Temperature

2013 ◽  
Vol 320 ◽  
pp. 483-487 ◽  
Author(s):  
Ming Li ◽  
Deng Bing Li ◽  
Jing Pan ◽  
Guang Hai Li
Keyword(s):  
Electron Microscopy ◽  
Phase Transition ◽  
Transition Temperature ◽  
Phase Transition Temperature ◽  
Variable Temperature ◽  
X Ray Diffraction ◽  
X Ray ◽  
Infrared Transmittance ◽  
Transmission Electron ◽  
Potential Applications

W-doped VO2 (B) nanoneedles were successfully synthesized by solgel combing with hydrothermal treatment, in which the polyethylene glycol (PEG) was used as both surfactant and reducing. The metastable VO2 (B) was completely transformed to thermochromic VO2 (M) after annealing at high purity N2 atmosphere. The DSC results exhibit a strong crystallographic transition, and the phase transition temperature of VO2 (M) can be reduced to about 38 °C by W-doping. Field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM) were used to characterize the morphology and crystalline structure of the samples. The variable-temperature infrared transmittance spectra of VO2 (M) demonstrate their potential applications in energy saving field.

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