Search results for "ta116"
showing 10 items of 942 documents
Crystal Structures and Density Functional Theory Calculations of o-and p-Nitroaniline Derivatives: Combined Effect of Hydrogen Bonding and aromatic i…
2013
The interplay of strong and weak hydrogen bonds, dipole–dipole interactions, and aromatic interactions of o- and p-nitroaniline derivatives was studied by combining crystal structure analysis and density functional theory (DFT) calculations. Crystal structures of four 2-nitroaniline derivatives, 2-((2-nitrophenyl)amino)ethyl methanesulfonate (1A), 2-((2-nitrophenyl)amino)ethyl 4-methylbenzenesulfonate (2A), N,N′-((1,3-phenylenebis(oxy))bis(ethane-2,1-diyl))bis(2-nitroaniline) (3A), and N-(2-chloroethyl)-2-nitroaniline (4A), and crystal structures of three 4-nitroaniline derivatives, 2-((4-nitrophenyl)amino)ethyl methanesulfonate (1B), 2-((4-nitrophenyl)amino)ethyl 4-methylbenzenesulfonate (…
Evidence of Weak Halogen Bonding: New Insights on Itraconazole and its Succinic Acid Cocrystal
2012
Exact knowledge of the crystal structure of drugs and lead compounds plays a significant role in the fields of crystal engineering, docking, computational modeling (drug–receptor interactions), and rational design of potent drugs in pharmaceutical chemistry. The succinic acid cocrystal of the systemic antifungal drug, itraconazole, reported by Remenar et al. (J. Am. Chem. Soc.2003, 125, 8456–8457) (CSD: IKEQEU), represents one of the classical examples displaying a molecular fitting mechanism in the solid state. In this work, we disclose the X-ray single-crystal structure of the cis-itraconazole–succinic acid (2:1) cocrystal and found that it differs slightly from the previously reported st…
Adsorption and Activation of Water on Cuboctahedral Rhodium and Platinum Nanoparticles
2017
Rh and Pt are widely used as the components in heterogeneous catalysts for multiple industrial applications. Because the metals are typically in the form of nanoparticles in real catalysts, it is important to carefully select models for the computational prediction of the catalytic properties. Here we report a first-principles study on the water activation, an important step in numerous catalytic reactions, using the finite-size Rh and Pt nanoparticle models and compare them to the extended surface models. We show that regardless of the model, adsorption and activation of water is practically identical for both metals, whereas the dissociation is energetically more favorable on Rh. The expe…
Iron and pH regulating the photochemical mineralization of dissolved organic carbon
2017
Solar radiation mineralizes dissolved organic matter (DOM) to dissolved inorganic carbon through photochemical reactions (DIC photoproduction) that are influenced by iron (Fe) and pH. This study addressed as to what extent Fe contributes to the optical properties of the chromophoric DOM (CDOM) and DIC photoproduction at different pH values. We created the associations of Fe and DOM (Fe-DOM) that cover the range of loadings of Fe on DOM and pH values found in freshwaters. The introduced Fe enhanced the light absorption by CDOM independent of pH. Simulated solar irradiation decreased the light absorption by CDOM (i.e., caused photobleaching). Fe raised the rate of photobleaching and steepened…
2-Methylresorcinarene: a very high packing coefficient in a mono-anion based dimeric capsule and the X-ray crystal structure of the tetra-anion
2016
Mono- and tetra-deprotonated 2-methylresorcinarene anions (1 and 2) as their trans-1,4-diammoniumcyclohexane (TDAC)2+ inclusion complexes are reported. The mono-anion forms a fully closed dimeric capsule [1·H2O·MeOH]22− with a cavity volume of 165 Å3 and (TDAC)2+ as the guest with an extremely high packing coefficient, PC = 84.2%, while the tetra-anion forms a close-packed structure with two structurally isomeric tetra-anions 2a and 2b with a 50 : 50 ratio in the crystal lattice. peerReviewed
Spin Crossover in Fe(II)–M(II) Cyanoheterobimetallic Frameworks (M = Ni, Pd, Pt) with 2-Substituted Pyrazines
2016
Discovery of spin-crossover (SCO) behavior in the family of Fe(II)-based Hofmann clathrates has led to a "new rush" in the field of bistable molecular materials. To date this class of SCO complexes is represented by several dozens of individual compounds, and areas of their potential application steadily increase. Starting from Fe(2+), square planar tetracyanometalates M(II)(CN)4(2-) (M(II) = Ni, Pd, Pt) and 2-substituted pyrazines Xpz (X = Cl, Me, I) as coligands we obtained a series of nine new Hofmann clathrate-like coordination frameworks. X-ray diffraction reveals that in these complexes Fe(II) ion has a pseudo-octahedral coordination environment supported by four μ4-tetracyanometallat…
Tunable Interaction Strength and Nature of the S···Br Halogen Bonds in [(Thione)Br2] Systems
2015
The strength and nature of the S···Br and Br···Br interactions were systematically tuned by altering the electron donor properties of the thione group. Three new halogen-bonded compounds, [(N-methylbenzothiazole-2-thione)Br2]·0.5CH2Cl2 (1), [(2(3H)-benzothiazolethione)Br2] (2), and [(2-benzimidazolethione)Br]·[Br3] (3), were synthesized and studied structurally by using X-ray crystallography and computationally by using charge density analysis based on QTAIM calculations. Analysis of the interaction strength indicated a formation of surprisingly strong S···Br halogen bonds in 1 (−104 kJ mol–1, and RBrS = 0.64) and 2 (−116 kJ mol–1, and RBrS = 0.63) with a substantial covalent contribution. …
An experimental and theoretical study of a heptacoordinated tungsten(VI) complex of a noninnocent phenylenediamine bis(phenolate) ligand
2018
Abstract [W(N2O2)(HN2O2)] (H4N2O2 = N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-phenylenediamine) with a noninnocent ligand was formed by reaction of the alkoxide precursor [W(eg)3] (eg = the 1,2-ethanediolate dianion) with two equivalents of ligand. The phenol groups on one of the ligands are completely deprotonated and the ligand coordinates in a tetradentate fashion, whereas the other ligand is tridentate with one phenol having an intact OH group. The molecular structure, magnetic measurements, EPR spectroscopy, and density functional theory calculations indicate that the complex is a stable radical with the odd electron situated on the tridentate amidophenoxide ligand. The formal ox…
Patterning of supported gold monolayers via chemical lift-off lithography
2017
The supported monolayer of Au that accompanies alkanethiolate molecules removed by polymer stamps during chemical lift-off lithography is a scarcely studied hybrid material. We show that these Au–alkanethiolate layers on poly(dimethylsiloxane) (PDMS) are transparent, functional, hybrid interfaces that can be patterned over nanometer, micrometer, and millimeter length scales. Unlike other ultrathin Au films and nanoparticles, lifted-off Au–alkanethiolate thin films lack a measurable optical signature. We therefore devised fabrication, characterization, and simulation strategies by which to interrogate the nanoscale structure, chemical functionality, stoichiometry, and spectral signature of t…
Strictly correlated electrons approach to excitation energies of dissociating molecules
2019
In this work we consider a numerically solvable model of a two-electron diatomic molecule to study a recently proposed approximation based on the density functional theory of so-called strictly correlated electrons (SCE). We map out the full two-particle wave function for a wide range of bond distances and interaction strengths and obtain analytic results for the two-particle states and eigenenergies in various limits of strong and weak interactions, and in the limit of large bond distance. We then study the so-called Hartree-exchange-correlation (Hxc) kernel of time-dependent density functional theory which is a key ingredient in calculating excitation energies. We study an approximation b…