scholarly journals A Super-Oxidized Radical Cationic Icosahedral Boron Cluster

2020 ◽  
Author(s):  
Julia M. Stauber ◽  
Josef Schwan ◽  
Xinglong Zhang ◽  
Jonathan C. Axtell ◽  
Dahee Jung ◽  
...  
Keyword(s):  
Electronic State ◽  
Unpaired Electron ◽  
Electrochemical Behavior ◽  
Spectroscopic Characterization ◽  
Open Shell ◽  
Chemical Oxidation ◽  
Neutral Species ◽  
X Ray ◽  
Boron Cluster ◽  
Reversible Redox

While the icosahedral closo-[B12H12]2– cluster does not display reversible electrochemical behavior, perfunctionalization of this species via substitution of all twelve B–H vertices with alkoxy orbenzyloxy (OR) substituents engenders reversible redox chemistry, providing access to clusters in the dianionic,monoanionic, and neutral forms. Here, we evaluated the electrochemical behavior of the electron-rich B12(O-3-methylbutyl)12 (1) cluster and discovered that a new reversible redox event that gives rise to a fourth electronic state is accessible through one-electron oxidation of the neutral species. Chemical oxidation of 1 with [N(2,4-Br2C6H3)3]•+ afforded the isolable[1] •+ cluster, which is the first example of an open-shell cationic B12 cluster in which the unpaired electron is proposed to be delocalized throughout the boron cluster core. The oxidation of 1 is also chemically reversible, where treatment of [1]•+ with ferrocene resulted in its reduction back to 1. The identity of [1]•+ is supported by EPR, UV-vis, multinuclear NMR (1H, 11B), and X-ray photoelectron spectroscopic characterization.<br>

scholarly journals A Super-Oxidized Radical Cationic Icosahedral Boron Cluster

2020 ◽  
Author(s):  
Julia M. Stauber ◽  
Josef Schwan ◽  
Xinglong Zhang ◽  
Jonathan C. Axtell ◽  
Dahee Jung ◽  
...  
Keyword(s):  
Electronic State ◽  
Unpaired Electron ◽  
Electrochemical Behavior ◽  
Spectroscopic Characterization ◽  
Open Shell ◽  
Chemical Oxidation ◽  
Neutral Species ◽  
X Ray ◽  
Boron Cluster ◽  
Reversible Redox

While the icosahedral closo-[B12H12]2– cluster does not display reversible electrochemical behavior, perfunctionalization of this species via substitution of all twelve B–H vertices with alkoxy orbenzyloxy (OR) substituents engenders reversible redox chemistry, providing access to clusters in the dianionic,monoanionic, and neutral forms. Here, we evaluated the electrochemical behavior of the electron-rich B12(O-3-methylbutyl)12 (1) cluster and discovered that a new reversible redox event that gives rise to a fourth electronic state is accessible through one-electron oxidation of the neutral species. Chemical oxidation of 1 with [N(2,4-Br2C6H3)3]•+ afforded the isolable[1] •+ cluster, which is the first example of an open-shell cationic B12 cluster in which the unpaired electron is proposed to be delocalized throughout the boron cluster core. The oxidation of 1 is also chemically reversible, where treatment of [1]•+ with ferrocene resulted in its reduction back to 1. The identity of [1]•+ is supported by EPR, UV-vis, multinuclear NMR (1H, 11B), and X-ray photoelectron spectroscopic characterization.<br>

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 4-[(2,4-Dichlorophenyl)carbamoyl]butanoic Acid

Molbank ◽  
10.3390/m1227 ◽  
2021 ◽  
Vol 2021 (2) ◽  
pp. M1227
Author(s):  
Bibi Hanifa ◽  
Muhammad Sirajuddin ◽  
Zafran Ullah ◽  
Sumera Mahboob ◽  
See Mun Lee ◽  
...  
Keyword(s):  
Torsion Angle ◽  
Acid Amide ◽  
Spectroscopic Characterization ◽  
Amide Bond ◽  
Amide Hydrogen ◽  
Butanoic Acid ◽  
X Ray ◽  
Amide Derivative

The synthesis and spectroscopic characterization of the glutaric acid-amide derivative, 2,4-Cl2C6H3N(H)C(=O)(CH2)3C(=O)OH (1), are described. The X-ray crystal structure determination of (1) shows the backbone of the molecule to be kinked about the methylene-C–N(amide) bond as seen in the C(p)–N–C(m)–C(m) torsion angle of −157.0(2)°; m = methylene and p = phenyl. An additional twist in the molecule is noted between the amide and phenyl groups as reflected in the C(m)–N–C(p)–C(p) torsion angle of 138.2(2)°. The most prominent feature of the molecular packing is the formation of supramolecular tapes assembled through carboxylic acid-O–H…O(carbonyl) and amide-N–H…O(amide) hydrogen bonding.

Synthesis, spectroscopic characterization, X-ray structure and magnetic properties of [Cu(hmquin-7-COOH)2(MeOH)] complex

Polyhedron ◽  
2009 ◽  
Vol 28 (17) ◽  
pp. 3774-3780 ◽  
Author(s):  
B. Machura ◽  
A. Świtlicka ◽  
J. Mroziński ◽  
J. Kłak ◽  
R. Kruszynski ◽  
...  
Keyword(s):  
Magnetic Properties ◽  
Spectroscopic Characterization ◽  
X Ray

Effect of Ligand on the Electronic State of Gold in Ligand-Protected Gold Clusters Elucidated by X-ray Absorption Spectroscopy

2021 ◽  
Vol 125 (5) ◽  
pp. 3143-3149
Author(s):  
Tomoki Matsuyama ◽  
Jun Hirayama ◽  
Yu Fujiki ◽  
Soichi Kikkawa ◽  
Wataru Kurashige ◽  
...  
Keyword(s):  
Electronic State ◽  
Absorption Spectroscopy ◽  
Gold Clusters ◽  
X Ray ◽  
X Ray Absorption

Eine elektrochemische und strukturelle Studie an den Eisensilylamiden Fe[N(SiMe3)2]2 und Fe[N(SiMe3)2]3 / An Electrochemical and Structural Study of the Iron Silylamides Fe[N(SiMe3)2]2 and Fe[N(SiMe3)2]3

2012 ◽  
Vol 67 (6) ◽  
pp. 549-556 ◽  
Author(s):  
Günter Margraf ◽  
Frauke Schödel ◽  
Inge Sänger ◽  
Michael Bolte ◽  
Matthias Wagner ◽  
...  
Keyword(s):  
Cyclic Voltammogram ◽  
X Ray Diffraction ◽  
Amido Complexes ◽  
X Ray ◽  
Redox Transition ◽  
Transfer Processes ◽  
Irreversible Oxidation ◽  
Reaction Solution ◽  
Reversible Redox ◽  
Electron Transfer Processes

The bis(trimethyl)silylamido complex Na(THF){Fe[N(SiMe3)2]3} and the disilane tBu3SiSitBu3 were obtained from the reaction of Fe[N(SiMe3)2]3 with the sodium silanide Na(THF)2[SitBu3] in a mixture of benzene and THF. Single crystals of Na(THF){Fe[N(SiMe3)2]3} suitable for X-ray diffraction were grown from the reaction solution at ambient temperature (orthorhombic, C2221, Z = 4). The solid-state structure features a contact-ion pair with two short N-Na contacts. The THF adducts {M(THF)2[N(SiMe3)2]2} reacted with 2,2´-bipyridine to give the corresponding complexes {M(2,2´bipy)[N(SiMe3)2]2} (M= Mn; Fe). Their structures (M= Fe: orthorhombic, Pca21, Z = 8; M = Mn: orthorhombic, Pbca, Z = 8) feature monomeric units. The cyclic voltammogram of Fe[N(SiMe3)2]3 revealed a reversible redox transition with the potential of -0;523 V (E½), which was assigned to the Fe(III)[N(SiMe3)2]3 → Fe(II)[N(SiMe3)2]-3 redox transition, whereas the compounds {Fe(THF)2[N(SiMe3)2]2} (Eox = -0;379 V) and {Fe(2,2´bipy)[N(SiMe3)2]2} (Eox = -0;436 V) featured irreversible oxidation waves. The related manganese bis(trimethylsilyl)amido complexes {Mn(THF)2[N(SiMe3)2]2} (Eox = -0;458 V) and {Mn(2,2´bipy)[N(SiMe3)2]2} (Eox = -0513 V) also underwent irreversibile electron transfer processes.

Structure and Electrochemical Behavior of Plasma-Sprayed LSGM Electrolyte Films

2002 ◽  
Vol 756 ◽  
Author(s):  
H. Zhang ◽  
X. Ma ◽  
J. Dai ◽  
S. Hui ◽  
J. Roth ◽  
...  
Keyword(s):  
Electrochemical Behavior ◽  
Electrochemical Impedance ◽  
Amorphous Structure ◽  
Solid Oxide ◽  
X Ray Diffraction ◽  
X Ray ◽  
Spray Process ◽  
Plasma Spray Process ◽  
Electrolyte Film ◽  
Plasma Sprayed

ABSTRACTAn intermediate temperature solid oxide fuel cell (SOFC) electrolyte film of La0.8Sr 0.2Ga0.8Mg0.2O2.8 (LSGM) was fabricated using a plasma spray process. The microstructure and phase were investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical behavior of the thermal sprayed LSGM film was investigated using electrochemical impedance spectroscopy (EIS). The study indicates that thermal spray can deposit a dense LSGM layer. It was found that the rapid cooling in the thermal process led to an amorphous or poor crystalline LSGM deposited layer. This amorphous structure has a significant effect on the performance of the cell. Crystallization of the deposited LSGM layer was observed during annealing between 500–600 °C. After annealing at 800 °C, the ionic conductivity of the sprayed LSGM layer can reach the same level as that of the sintered LSGM.

scholarly journals 151Eu Mössbauer Spectroscopic Characterization of EuRu4B4 and the New Boride EuRuB4

2010 ◽  
Vol 65 (1) ◽  
pp. 90-94 ◽  
Author(s):  
Thomas Harmening ◽  
Rainer Pöttgen
Keyword(s):  
Boron Atom ◽  
Mössbauer Spectra ◽  
Induction Furnace ◽  
Spectroscopic Characterization ◽  
Two Dimensional ◽  
Temperature Dependent ◽  
X Ray ◽  
Trivalent Europium ◽  
Mossbauer Spectra

Samples of EuRu4B4 and of the new boride EuRuB4 were prepared from europium, RuB, and RuB4 precursor alloys, respectively, in sealed tantalum tubes in an induction furnace. EuRu4B4 crystallizes with the LuRu4B4 structure, a = 748.1(1), c = 1502.3(4) pm. The structure of EuRuB4 was refined on the basis of X-ray diffractometer data: Pbam, a = 599.7(1), b = 1160.7(3), c = 358.06(7) pm, wR2 = 0.0691, 474 F2 values, and 38 variables. The four crystallographically independent boron sites build up layers which consist of almost regular pentagons and heptagons which sandwich the ruthenium and europium atoms, respectively. Within the two-dimensional [B4] networks each boron atom has a slightly distorted trigonal-planar boron coordination with B-B distances in the range 172 - 186 pm. Temperature-dependent 151Eu Mössbauer spectra show stable trivalent europium for EuRu4B4 and EuRuB4

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