scholarly journals Cyclopentadienyl coordination induces unexpected ionic Am−N bonding in an americium bipyridyl complex

2022 ◽  
Vol 13 (1) ◽  
Author(s):  
Brian N. Long ◽  
María J. Beltrán-Leiva ◽  
Cristian Celis-Barros ◽  
Joseph M. Sperling ◽  
Todd N. Poe ◽  
...  
Keyword(s):  
Spent Nuclear Fuel ◽  
Theoretical Calculations ◽  
Spectroscopic Properties ◽  
Spectroscopic Techniques ◽  
X Ray Diffraction ◽  
Coordination Environment ◽  
Trivalent Lanthanides ◽  
Key Factor ◽  
Bipyridyl Complex

AbstractVariations in bonding between trivalent lanthanides and actinides is critical for reprocessing spent nuclear fuel. The ability to tune bonding and the coordination environment in these trivalent systems is a key factor in identifying a solution for separating lanthanides and actinides. Coordination of 4,4′−bipyridine (4,4′−bpy) and trimethylsilylcyclopentadienide (Cp′) to americium introduces unexpectedly ionic Am−N bonding character and unique spectroscopic properties. Here we report the structural characterization of (Cp′3Am)2(μ − 4,4′−bpy) and its lanthanide analogue, (Cp′3Nd)2(μ − 4,4′−bpy), by single-crystal X-ray diffraction. Spectroscopic techniques in both solid and solution phase are performed in conjunction with theoretical calculations to probe the effects the unique coordination environment has on the electronic structure.

scholarly journals Synthesis, Crystal Structures, and Spectroscopic Characterization of Bis-aldehyde Monomers and Their Electrically Conductive Pristine Polyazomethines

Polymers ◽  
2019 ◽  
Vol 11 (9) ◽  
pp. 1498 ◽  
Author(s):  
Abdul Hafeez ◽  
Zareen Akhter ◽  
John F. Gallagher ◽  
Nawazish Ali Khan ◽  
Asghari Gul ◽  
...  
Keyword(s):  
Electrical Conductivity ◽  
Spectroscopic Characterization ◽  
Spectroscopic Techniques ◽  
Conductivity Measurements ◽  
X Ray Diffraction ◽  
Electrically Conductive ◽  
X Ray ◽  
Vis Spectroscopy ◽  
Ft Ir

Bis-aldehyde monomers 4-(4′-formyl-phenoxy)benzaldehyde (3a), 3-methoxy-4-(4′-formyl-phenoxy)benzaldehyde (3b), and 3-ethoxy-4-(4′-formyl-phenoxy)benzaldehyde (3c) were synthesized by etherification of 4-fluorobenzaldehyde (1) with 4-hydroxybenzaldehyde (2a), 3-methoxy-4-hydroxybenzaldehyde (2b), and 3-ethoxy-4-hydroxybenzaldehyde (2c), respectively. Each monomer was polymerized with p-phenylenediamine and 4,4′-diaminodiphenyl ether to yield six poly(azomethine)s. Single crystal X-ray diffraction structures of 3b and 3c were determined. The structural characterization of the monomers and poly(azomethine)s was performed by FT-IR and NMR spectroscopic techniques and elemental analysis. Physicochemical properties of polymers were investigated by powder X-ray diffraction, thermogravimetric analysis (TGA), viscometry, UV–vis, spectroscopy and photoluminescence. These polymers were subjected to electrical conductivity measurements by the four-probe method, and their conductivities were found to be in the range 4.0 × 10−5 to 6.4 × 10−5 Scm−1, which was significantly higher than the values reported so far.

Crystal structure, thermodynamic properties and detonation characterization of bis(5-amino-1,2,4-triazol-3-yl)methane

2020 ◽  
Vol 76 (1) ◽  
pp. 64-68 ◽  
Author(s):  
Hongya Li ◽  
Biao Yan ◽  
Haixia Ma ◽  
Zhiyong Sun ◽  
Yajun Ma ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Detonation Velocity ◽  
Theoretical Calculations ◽  
Detonation Pressure ◽  
X Ray Diffraction ◽  
X Ray ◽  
Equivalent Equation ◽  
Experimental Values ◽  
Experimental Density

Bis(5-amino-1,2,4-triazol-3-yl)methane (BATZM, C5H8N8) was synthesized and its crystal structure characterized by single-crystal X-ray diffraction; it belongs to the space group Fdd2 (orthorhombic) with Z = 8. The structure of BATZM can be described as a V-shaped molecule with reasonable chemical geometry and no disorder. The specific molar heat capacity (Cp,m ) of BATZM was determined using the continuous Cp mode of a microcalorimeter and theoretical calculations, and the Cp,m value is 211.19 J K−1 mol−1 at 298.15 K. The relative deviations between the theoretical and experimental values of Cp,m , HT – H 298.15K and ST – S 298.15K of BATZM are almost equivalent at each temperature. The detonation velocity (D) and detonation pressure (P) of BATZM were estimated using the nitrogen equivalent equation according to the experimental density; BATZM has a higher detonation velocity (7954.87 ± 3.29 m s−1) and detonation pressure (25.72 ± 0.03 GPa) than TNT.

Synthesis and characterization of novel poly(HAzPMA-co-SA)/RDX/CdS nanocomposite as a polymer bonded explosive

2020 ◽  
Vol 98 (12) ◽  
pp. 755-763
Author(s):  
Hamid Reza Ghayeni ◽  
Reza Razeghi ◽  
Abolfazl Olyaei
Keyword(s):  
Uv Light ◽  
Light Exposure ◽  
Sodium Acrylate ◽  
Spectroscopic Techniques ◽  
Effective Parameters ◽  
X Ray Diffraction ◽  
X Ray ◽  
Cds Nanorods ◽  
Transmission Electron

Cadmium sulfide nanorods with a length of 69 nm have been prepared by using Cd(OAc)2.2H2O and S8 at 125 °C in the presence of triethylenetetramine as the template agent and coordination agent and characterized by using X-ray diffraction, transmission electron microscopy, FTIR, photoluminescence, and UV–vis absorption spectroscopic techniques. Photocopolymerization of glycidyl methacrylate (GMA) and sodium acrylate (SA) was carried out using CdS nanorods as a photocatalyst under UV light exposure at 400 nm in the presence of β-cyclodextrin (β-CD). To optimization of the effective parameters on the synthesis of copolymer nanocomposite, the amounts of initiator, monomers, and β-CD, duration of pre-deoxygenation, and light wavelength were evaluated. Ring opening of poly(GMA-co-SA)/CdS nanocomposite with NaN3 afforded poly(HAzPMA-co-SA)/CdS nanocomposite and subsequent mixing with RDX in DMF led to the formation of poly(HAzPMA-co-SA)/RDX/CdS nanocomposite as a polymer bonded explosive. All of the copolymer nanocomposites were characterized using various tools of instrumental analysis.

Preparation and Characterization of TiO2 Nanostructures for Catalytic CO2 Photoconversion

2011 ◽  
Vol 183 ◽  
pp. 89-94 ◽  
Author(s):  
Anna Iwulska ◽  
G. Sliwinski
Keyword(s):  
Active Surface ◽  
Laser Pulses ◽  
Point Of View ◽  
Deep Penetration ◽  
Spectroscopic Techniques ◽  
X Ray Diffraction ◽  
X Ray ◽  
Content Ratio ◽  
Photocatalytic Applications

The titanium dioxide target (99.7%) of 1 cm in dia was ablated in vacuum by laser pulses (6 ns) at 266 nm and at repetition rate of 10 Hz. During deposition the laser fluence between 1 and 3.5 J/cm2 and the O2 pressure from the range of 10-2 – 1 Pa were applied. The thin TiO2 films were deposited on glass substrate (1 × 1 cm2) heated up to 500 °C. The chemical composition of the film and samples produced by annealing were investigated by spectroscopic techniques (μ-Raman, EDX) and the structure, porosity and surface morphology were analysed by means of SEM and x-ray diffraction (XRD). The SEM inspection of the TiO2 thin film samples indicates that the obtained material is mostly crystalline. After annealing in O2 at 500 °C the structure characterized by the presence of both anatase and rutile phases is observed in the Raman spectra and confirmed by the XRD data. The phase content ratio depends on the O2 pressure applied. Results confirm that nanostructures produced in this way represent densely packed columns and promote deep penetration of guest particles such as CO2.The resulting large active surface is advantageous from the point of view of photocatalytic applications.

scholarly journals Estudo do tautomerismo ceto-enólico da 7-epi-clusianona através de cálculos teóricos de deslocamentos químicos de RMN

2020 ◽  
Author(s):  
Ana Carolina Ferreira de Albuquerque ◽  
José Walkimar de Mesquita Carneiro ◽  
Fernando Martins dos Santos Junior
Keyword(s):  
Natural Products ◽  
Structural Characterization ◽  
Density Functional ◽  
Theoretical Calculations ◽  
Chemical Shifts ◽  
Coupling Constants ◽  
Spectroscopic Techniques ◽  
Chemical Structures ◽  
Nmr Parameters

The properties of natural products, including their biological and pharmacological activities, are directly correlated with their chemical structures. Thus, a correct structural characterization of these compounds is a crucial step to the understanding of their biological activities. However, despite the recent advances in spectroscopic techniques, structural studies of natural products can be challenging. This way, theoretical calculations of Nuclear Magnetic Resonance (NMR) parameters (such as chemical shifts and coupling constants) have proven to be a powerful and low-cost tool for the aid to experimental techniques traditionally used for the structural characterization of natural products. One of the several applications of quantum-mechanical calculations of NMR parameters is the study of tautomerism. Since chemical shifts are sensitive to the tautomeric equilibrium, this technique can provide crucial informations. In this work, it was applied a protocol for theoretical calculations of ¹³C chemical shifts in order to study the tautomerism of the natural product 7-epi-clusianone, isolated from Rheedia gardneriana. This protocol consists in a Monte Carlo conformational search, followed by geometry optimization and shielding tensors calculations, both using a density functional level of theory. After comparison of theoretical and experimental data, it was possible to confirm the two tautomers present in equilibrium in the experimental solution. Furthermore, this study highlights how this theoretical protocol can be an effective method in identifying the preferred tautomeric form in solution.

Crystal structure, thermal properties and detonation characterization of bis(5-amino-1,2,4-triazol-4-ium-3-yl)methane dichloride

2020 ◽  
Vol 76 (8) ◽  
pp. 821-827
Author(s):  
Hongya Li ◽  
Biao Yan ◽  
Haixia Ma ◽  
Xiangrong Ma ◽  
Zhiyong Sun ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Detonation Velocity ◽  
Theoretical Calculations ◽  
Dimensional Structure ◽  
Detonation Pressure ◽  
X Ray Diffraction ◽  
Equivalent Equation ◽  
Experimental Values ◽  
Experimental Density

Bis(5-amino-1,2,4-triazol-4-ium-3-yl)methane dichloride (BATZM·Cl2 or C5H10N8 2+·2Cl−) was synthesized and crystallized, and the crystal structure was characterized by single-crystal X-ray diffraction; it belongs to the space group C2/c (monoclinic) with Z = 4. The structure of BATZM·Cl2 can be described as a V-shaped molecule with reasonable chemical geometry and no disorder, and its one-dimensional structure can be described as a rhombic helix. The specific molar heat capacity (Cp ,m) of BATZM·Cl2 was determined using the continuous C p mode of a microcalorimeter and theoretical calculations, and the Cp ,m value is 276.18 J K−1 mol−1 at 298.15 K. The relative deviations between the theoretical and experimental values of Cp ,m, HT – H 298.15K and ST – S 298.15K of BATZM·Cl2 are almost equivalent at each temperature. The detonation velocity (D) and detonation pressure (P) of BATZM·Cl2 were estimated using the nitrogen equivalent equation according to the experimental density; BATZM·Cl2 has a higher detonation velocity (7143.60 ± 3.66 m s−1) and detonation pressure (21.49 ± 0.03 GPa) than TNT. The above results for BATZM·Cl2 are compared with those of bis(5-amino-1,2,4-triazol-3-yl)methane (BATZM) and the effect of salt formation on them is discussed.

Synthesis, crystal structure and physicochemical characterization of a Hg(II) complex with 6-methoxyquinoline as ligand

2015 ◽  
Vol 70 (10) ◽  
pp. 719-725 ◽  
Author(s):  
Cristian Villa-Pérez ◽  
Isabel C. Ortega ◽  
Angélica M. Payán-Aristizábal ◽  
Gustavo Echeverría ◽  
Gloria C. Valencia-Uribe ◽  
...  
Keyword(s):  
Molecular Oxygen ◽  
Theoretical Calculations ◽  
Physicochemical Characterization ◽  
Spectroscopic Studies ◽  
Monoclinic Space Group ◽  
Oxygen Production ◽  
X Ray Diffraction ◽  
Singlet Molecular Oxygen ◽  
X Ray

AbstractA new complex of Hg(II) with 6-methoxyquinoline (C10H9NO-6MQ) has been synthesized and characterized. The structure of the complex Hg(6MQ)Cl2 was determined by single crystal X-ray diffraction. It crystallizes in the monoclinic space group P21/c with a = 3.9139(3), b = 26.3400(2), c = 10.9090(9) Å, β = 89.833(6)°, V = 1124.6(1) Å3 and Z = 4 molecules per unit cell. The coordination geometry of the mercury(II) center can be described as a distorted square pyramid formed by one nitrogen atom of the 6MQ and four chlorine atoms. Fourier transform infrared, Raman and UV/Vis spectroscopic studies have been carried out to characterize the compound, using theoretical calculations for the assignment of the experimentally observed bands. The thermal behavior was investigated by thermogravimetric analysis. The quantum yield of singlet molecular oxygen production ΦΔ was measured with steady-state methods in ethanol, using 9,10-dimethylanthracene (DMA) as actinometer and Bengal rose as reference photosensitizer. The resultant singlet molecular oxygen was detected indirectly by photooxidation reactions of DMA. The luminescence properties have also been studied.

Molecular and X-ray Spectroscopies for Noninvasive Characterization of Mayan Green Stones from Bonampak, Chiapas

2019 ◽  
Vol 73 (9) ◽  
pp. 1074-1086
Author(s):  
Valentina Aguilar-Melo ◽  
Alejandro Mitrani ◽  
Edgar Casanova-Gonzalez ◽  
Mayra D. Manrique-Ortega ◽  
Griselda Pérez-Ireta ◽  
...  
Keyword(s):  
Archaeological Site ◽  
Molecular Techniques ◽  
Spectroscopic Techniques ◽  
X Ray Diffraction ◽  
X Ray ◽  
Ft Ir ◽  
Noninvasive Characterization ◽  
A Minor

A burial and a rich offering were found under Room 2 in the Murals Building, Bonampak, a Mayan archaeological site situated in Chiapas, Mexico. This burial may be related with the creation of the famous mural paintings. A rich set of jewelry made of green stones was among the different objects found. Green stones have great importance in Mesoamerican cultures, those composed of jadeite being the most appreciated. To characterize the green stones, different spectroscopic techniques were used in a complementary way: Raman and infrared spectroscopies (FT-IR) were used for global mineralogical analysis, while X-ray diffraction (XRD) and X-ray fluorescence (XRF) were applied simultaneously in situ on the artifacts that were not successfully identified by these molecular techniques. In addition, XRF was used to contrasts the elemental information from pieces composed of pyroxenes that may be related to the raw sources of jade in Guatemala. The main minerals identified within the beads and earrings were jadeite with omphacite and jadeite with albite; to a minor extent, quartz, and serpentine. In this paper, the main features of the molecular and X-ray techniques are compared in order to determine the advantages and limitations of these spectroscopies for mineral identification. With this combination of techniques, it was possible to undertake a suitable characterization of the analyzed objects. This paper focuses on the XRD–XRF combined analysis for in situ noninvasive characterization.

scholarly journals STRUCTURAL CHARACTERIZATION OF 2-AMINO-2-OXOACETIC ACID BY X-RAY POWDER DIFFRACTION AND QUANTUM CHEMISTRY

2019 ◽  
Vol 16 (33) ◽  
pp. 516-523
Author(s):  
G. E. DELGADO ◽  
L. M. BELANDRIA ◽  
M. GUILLEN ◽  
A.. J. MORA ◽  
L. E. SEIJAS
Keyword(s):  
Hydrogen Bonds ◽  
Single Crystal ◽  
Structural Study ◽  
Powder Diffraction ◽  
Structural Characterization ◽  
Structure Determination ◽  
Spectroscopic Techniques ◽  
X Ray Diffraction ◽  
X Ray

2-amino-2-oxoacetic acid, carbamoyl formic acid, or oxamic acid is an active pharmaceutical ingredient (API) of great importance mainly because is an inhibitor of lactic dehydrogenase (LDH). It acts as an inhibitor to the metabolic pathways of the tumor cells and exhibited significant anticancer activity against nasopharyngeal carcinoma (NPC) cells in vitro and can be considered as a potential drug for the treatment of type 2 diabetes. Also, this compound could be used as a building block in the design of supramolecular architectures based on hydrogen bonds through the complimentary hydrogen-bond functionalities of the carbonyl and amide functional groups present. Single-crystal X-ray diffraction is the most powerful technique for crystal structure determination of small molecules. However, for several materials, including oxamic acid, it could be complicated to grow single crystals of suitable size and quality that make them appropriated to structure analysis. For this reason, the structural study was conducted with powder X-ray diffraction which is a process significantly more challenging than structure determination from single-crystal data. Oxamic acid has been characterized by FT-IR and NMR spectroscopic techniques, thermal TGA-DSC analysis, semi-empirical PM7 calculations, and X-ray powder diffraction. The title compound crystallizes in the monoclinic system with space group Cc, Z=4, and unit cell parameters a= 9.4994(4) Å, b= 5.4380(2) Å, c= 6.8636(3) Å, b= 107.149(2)°, V= 338.79(2) Å3. The molecule has a trans conformation. The molecular structure and crystal packing are stabilized mainly by intra- and intermolecular O--H···O and N--H···O hydrogen bonds. The structural characterization of this type of API compound is important to understand its mechanisms of action due to its considerable biological effects. In particular, for oxamic acid, this structural study would allow subsequent examination of its medicinal properties as an antitumor and antidiabetic agent.

scholarly journals Synthesis and structural analysis of polynuclear silver(I) complexes with 4,7-phenanthroline

2019 ◽  
Vol 84 (7) ◽  
pp. 689-699 ◽  
Author(s):  
Ivana Stanojevic ◽  
Nada Savic ◽  
Aurélien Crochet ◽  
Katharina Fromm ◽  
Milos Djuran ◽  
...  
Keyword(s):  
Solid State ◽  
Room Temperature ◽  
Volume Ratio ◽  
Spectroscopic Techniques ◽  
X Ray Diffraction ◽  
X Ray ◽  
Bridging Ligand ◽  
Coordination Sites ◽  
Hydrolysis Of

New polynuclear silver(I) complexes, [Ag(CF3SO3)(4,7-phen)(CH3CN)]n (1) and [Ag(PO2F2)(4,7-phen)]n (2), were synthesized by the reaction of 4,7-phenanthroline (4,7-phen) and the corresponding AgX salt (X = CF3SO3 - and PF6 -) in 1:2 mole ratio, respectively, in methanol/acetone (1:1 volume ratio) at room temperature. The characterization of the complexes was established on the basis of elemental microanalysis, IR and NMR (1H and 13C) spectroscopic techniques, while their crystal structures were determined by single-crystal X-ray diffraction analysis. The results of spectroscopic and crystallographic analyses revealed that in these complexes, 4,7-phen behaves as a bridging ligand between two metal ions, while the remaining coordination sites of the Ag(I) ions are occupied by the oxygen atom of CF3SO3 - and an acetonitrile nitrogen atom in 1 or by two oxygen atoms from two PO2F2 -, formed after hydrolysis of PF6 -, in 2. In the solid state, both complexes are coordination polymers in which the geometry around the Ag(I) ions is distorted tetrahedral.

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