Reaction of the Five-Coordinate O-Nitrito Complex Fe(Por)(ONO) (Por = meso-tetra-arylporphyrinato) with THF Gives Two Six-Coordinate Isomers

2009 ◽  
Vol 62 (10) ◽  
pp. 1226 ◽  
Author(s):  
Tigran S. Kurtikyan ◽  
Astghik A. Hovhannisyan ◽  
Alexei Iretskii ◽  
Peter C. Ford
Keyword(s):  
Low Temperature ◽  
Density Functional ◽  
Adduct Formation ◽  
Solvent Free ◽  
Model Systems ◽  
Lewis Bases ◽  
Nitrogen Donor ◽  
Density Functional Computations

The effect of the proximal ligand on the coordination of the nitrite ligand to the heme model systems Fe(Por)(η1-ONO) (Por = meso-tetraarylporphyrinato dianion) was investigated by FTIR and UV-vis spectra in solvent free, low temperature, porous layered solids and by density functional computations. The reaction of the five-coordinate complex Fe(Por)(η1-ONO) with the ether tetrahydrofuran gives a mixture of the O-nitrito and N-nitrito isomers Fe(Por)(THF)(η1-ONO) and Fe(Por)(THF)(NO2), respectively. This observation is in contrast to earlier studies with nitrogen donor Lewis bases where the N-nitrito isomers were clearly the more stable of the six-coordinated complexes. The adduct formation is reversible; the five-coordinate O-nitrito complexes Fe(Por)(η1-ONO) were largely restored upon warming under vacuum pumping.

scholarly journals Structural Analysis and Reactivity of Tetramethylcopper(III) Complex towards Nitrogen Donor Ligands by Density Functional Theory

2016 ◽  
Vol 2016 ◽  
pp. 1-8
Author(s):  
Perumal Balu ◽  
Venu Kannappan ◽  
Rathinavelu Kumar
Keyword(s):  
Density Functional ◽  
Structural Parameters ◽  
Population Analysis ◽  
Model Systems ◽  
Basis Set ◽  
Donor Ligands ◽  
Energy Decomposition Analysis ◽  
Chemical Hardness ◽  
Nitrogen Donor Ligands ◽  
Nitrogen Donor

DFT studies are carried out on some ligand substitution reactions of tetramethylcuprate(III) (TMC) complex with five different nitrogen donor ligands as probe ligands. The geometry optimization of the possible nine model systems and the frequency calculations are carried out at DFT level using LANL2DZ basis set. The selected structural parameters of optimized model systems of Cu(III) complexes are reported and discussed. The change in the M-C bond distance in TMC due to substitution by probe ligands is explained. Natural population analysis (NPA) has been carried out for these complexes to establish the charge of copper in these complexes. A detailed population analysis of valence orbitals of copper complexes supports the existence of d8 configuration for metal in complexes and there is evidence for the transmission of electrons from the nitrogen donor atom to dxy, dx2-y2, and 4s orbitals. Bond order calculations have been performed for all the complexes to probe the interaction between Cu(III) and the ligand. The stability of the complexes is ascertained from the computed chemical hardness. In order to understand the nature of Cu(III)-L (L = N donors) and Cu(III)-Me bonds in different complexes, Energy Decomposition Analysis (EDA) has been carried out for all the complexes chosen in the theoretical study. Thermodynamic feasibility of these reactions is investigated in terms of free energy changes of these reactions.

A Solvent Free Synthetic Route for Cerium(IV) Metal-Organic Frame-works with UiO-66 Architecture and Their Photocatalytic Application

2019 ◽  
Author(s):  
Matteo Campanelli ◽  
Tiziana Del Giacco ◽  
Filippo De Angelis ◽  
Edoardo Mosconi ◽  
Marco Taddei ◽  
...  
Keyword(s):  
Density Functional ◽  
Chemical Oxidation ◽  
Solvent Free ◽  
Cerium Ammonium Nitrate ◽  
Benzylic Alcohols ◽  
Near Ultraviolet ◽  
Photocatalytic Application ◽  
Activity Density ◽  
Ultraviolet Light Irradiation ◽  
Metal Organic

<div> <p>A novel solvent-free synthesis for Ce-UiO-66 metal-organic frameworks (MOFs) is presented. The MOFs are obtained by simply grinding the reagents, cerium ammonium nitrate (CAN) and the carboxylic linkers, in a mortar for few minutes with the addition of a small amount of acetic acid (AcOH) as modulator (1.75 eq, o.1 ml). The slurry is then transferred into a 1 ml vial and heated at 120°C for 1 day. The MOFs have been characterized for their composition, crystallinity and porosity and employed as heterogenous catalysts for the photo-oxidation reaction of substituted benzylic alcohols to benzaldaldehydes under near ultraviolet light irradiation. The catalytic performances, such as yield, conversion and kinetics, exceed those of similar systems studied by chemical oxidation and using Ce-MOF as catalyst. Moreover, the MOFs were found to be reusable up to three cycles without loss of activity. Density functional theory (DFT) calculations gave an estimation of the band-gap shift due to the different nature of the linkers used and provide useful information on the catalytic activity experimentally observed.</p> </div>

scholarly journals Band degeneracy enhanced thermoelectric performance in layered oxyselenides by first-principles calculations

2021 ◽  
Vol 7 (1) ◽  
Author(s):  
Ning Wang ◽  
Menglu Li ◽  
Haiyan Xiao ◽  
Zhibin Gao ◽  
Zijiang Liu ◽  
...  
Keyword(s):  
Density Functional ◽  
Transport Theory ◽  
Relaxation Times ◽  
Wide Band ◽  
Type Systems ◽  
Model Systems ◽  
Boltzmann Transport ◽  
Seebeck Coefficients ◽  
Boltzmann Transport Theory ◽  
P Type

AbstractBand degeneracy is effective in optimizing the power factors of thermoelectric (TE) materials by enhancing the Seebeck coefficients. In this study, we demonstrate this effect in model systems of layered oxyselenide family by the density functional theory (DFT) combined with semi-classical Boltzmann transport theory. TE transport performance of layered LaCuOSe and BiCuOSe are fully compared. The results show that due to the larger electrical conductivities caused by longer electron relaxation times, the n-type systems show better TE performance than p-type systems for both LaCuOSe and BiCuOSe. Besides, the conduction band degeneracy of LaCuOSe leads to a larger Seebeck coefficient and a higher optimal carrier concentration than n-type BiCuOSe, and thus a higher power factor. The optimal figure of merit (ZT) value of 1.46 for n-type LaCuOSe is 22% larger than that of 1.2 for n-type BiCuOSe. This study highlights the potential of wide band gap material LaCuOSe for highly efficient TE applications, and demonstrates that inducing band degeneracy by cations substitution is an effective way to enhance the TE performance of layered oxyselenides.

Adduct Formation of Dichloridodioxidomolybdenum(VI) and Methyltrioxidorhenium(VII) with a Series of Bidentate Nitrogen Donor Ligands

2009 ◽  
Vol 2009 (8) ◽  
pp. 1019-1026 ◽  
Author(s):  
Ahmad M. Al-Ajlouni ◽  
Alev Günyar ◽  
Ming-Dong Zhou ◽  
Paul N. W. Baxter ◽  
Fritz E. Kühn
Keyword(s):  
Adduct Formation ◽  
Donor Ligands ◽  
Nitrogen Donor Ligands ◽  
Nitrogen Donor

scholarly journals Unique structure of active platinum-bismuth site for oxidation of carbon monoxide

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Bing Nan ◽  
Qiang Fu ◽  
Jing Yu ◽  
Miao Shu ◽  
Lu-Lu Zhou ◽  
...  
Keyword(s):  
Carbon Monoxide ◽  
Low Temperature ◽  
Co Oxidation ◽  
Density Functional ◽  
Technology Development ◽  
Co Adsorption ◽  
Combustion Engines ◽  
Advanced Combustion ◽  
Surface Metal ◽  
Bismuth Cluster

AbstractAs the technology development, the future advanced combustion engines must be designed to perform at a low temperature. Thus, it is a great challenge to synthesize high active and stable catalysts to resolve exhaust below 100 °C. Here, we report that bismuth as a dopant is added to form platinum-bismuth cluster on silica for CO oxidation. The highly reducible oxygen species provided by surface metal-oxide (M-O) interface could be activated by CO at low temperature (~50 °C) with a high CO2 production rate of 487 μmolCO2·gPt−1·s−1 at 110 °C. Experiment data combined with density functional calculation (DFT) results demonstrate that Pt cluster with surface Pt−O−Bi structure is the active site for CO oxidation via providing moderate CO adsorption and activating CO molecules with electron transformation between platinum atom and carbon monoxide. These findings provide a unique and general approach towards design of potential excellent performance catalysts for redox reaction.

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.

scholarly journals Simulation of bonding effects in HRTEM images of light element materials

2011 ◽  
Vol 2 ◽  
pp. 394-404 ◽  
Author(s):  
Simon Kurasch ◽  
Jannik C Meyer ◽  
Daniela Künzel ◽  
Axel Groß ◽  
Ute Kaiser
Keyword(s):  
Density Functional ◽  
Structural Information ◽  
Hexagonal Boron Nitride ◽  
Light Element ◽  
Model Systems ◽  
Single Atom ◽  
Transmission Electron ◽  
Relative Contrast ◽  
Oxygen Substitution ◽  
Simulation Scheme

The accuracy of multislice high-resolution transmission electron microscopy (HRTEM) simulation can be improved by calculating the scattering potential using density functional theory (DFT) Gemming, T.; Möbus, G.; Exner, M.; Ernst, F.; Rühle, M. J. Microsc. 1998, 190, 89–98. doi:10.1046/j.1365-2818.1998.3110863.xDeng, B.; Marks, L. D. Acta Crystallogr., Sect. A 2006, 62, 208–216. doi:10.1107/S010876730601004X. This approach accounts for the fact that electrons in the specimen are redistributed according to their local chemical environment. This influences the scattering process and alters the absolute and relative contrast in the final image. For light element materials with well defined geometry, such as graphene and hexagonal boron nitride monolayers, the DFT based simulation scheme turned out to be necessary to prevent misinterpretation of weak signals, such as the identification of nitrogen substitutions in a graphene network. Furthermore, this implies that the HRTEM image does not only contain structural information (atom positions and atomic numbers). Instead, information on the electron charge distribution can be gained in addition. In order to produce meaningful results, the new input parameters need to be chosen carefully. Here we present details of the simulation process and discuss the influence of the main parameters on the final result. Furthermore we apply the simulation scheme to three model systems: A single atom boron and a single atom oxygen substitution in graphene and an oxygen adatom on graphene.

scholarly journals Nanoribbons with Non-Alternant Topology from Fusion of Polyazulene: Carbon Allotropes Beyond Graphene

2019 ◽  
Author(s):  
Qitang Fan ◽  
Daniel Martin-Jimenez ◽  
Daniel Ebeling ◽  
Claudio K. Krug ◽  
Lea Brechmann ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Low Temperature ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Scanning Probe ◽  
Two Dimensional ◽  
Reaction Step ◽  
Functional Theory ◽  
Carbon Allotropes ◽  
Temperature Scanning

Various two-dimensional (2D) carbon allotropes with non-alternant topologies, such as pentaheptites and phagraphene, have been proposed. Predictions indicate that these metastable carbon polymorphs, which contain odd-numbered rings, possess unusual (opto)electronic properties. However, none of these materials has been achieved experimentally due to synthetic challenges. In this work, by using on-surface synthesis, nanoribbons of the non-alternant graphene allotropes, phagraphene and tetra-penta-hepta(TPH)-graphene have been obtained by dehydrogenative C-C coupling of 2,6-polyazulene chains. These chains were formed in a preceding reaction step via on-surface Ullmann coupling of 2,6-dibromoazulene. Low-temperature scanning probe microscopies with CO-functionalized tip and density functional theory calculations have been used to elucidate their structural properties. <br>

scholarly journals Low-temperature and purification-free stereocontrolled ring-opening polymerisation of lactide in supercritical carbon dioxide

2020 ◽  
Vol 22 (7) ◽  
pp. 2197-2202 ◽  
Author(s):  
Simon P. Bassett ◽  
Andrew D. Russell ◽  
Paul McKeown ◽  
Isabel Robinson ◽  
Thomas R. Forder ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Low Temperature ◽  
Supercritical Carbon Dioxide ◽  
Ring Opening ◽  
Solvent Free ◽  
Free Ring ◽  
First Time ◽  
Supercritical Carbon

A stereoselective, solvent-free ring-opening polymerisation (ROP) of lactide (LA) in supercritical carbon dioxide (scCO2) is reported for the first time.

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