Electronic structure of Nd1-xYxMnO3 from Mn K edge absorption spectroscopy and DFT methods

The electronic structure of Nd1-xYxMnO3 (x-0-0.5) is studied using x-ray absorption near-edge structure (XANES) spectroscopy at the Mn K-edge along with the DFT-based LSDA+U and real space cluster calculations. The main edge of the spectra does not show any variation with doping. The pre-edge shows two distinct features which appear well-separated with doping. The intensity of the pre-edge decreases with doping. The theoretical XANES were calculated using real space multiple scattering methods which reproduces the entire experimental spectra at the main edge as well as the pre-edge. Density functional theory calculations are used to obtain the Mn 4p, Mn 3d and O 2p density of states. For x=0, the site-projected density of states at 1.7 eV above Fermi energy shows a singular peak of unoccupied e(g) (spin-up) states which is hybridized Mn 4p and O 2p states. For x=0.5, this feature develops at a higher energy and is highly delocalized and overlaps with the 3d spin-down states which changes the pre-edge intensity. The Mn 4p DOS for both compositions, show considerable difference between the individual p(x), p(y) and p(z)), states. For x=0.5, there is a considerable change in the 4p orbital polarization suggesting changes in the Jahn-Teller effect with doping. (C) 2013 Elsevier Ltd. All rights reserved.

New luminescent 2-methoxy-6-(4-methoxy-phenyl)-4-p-tolyl-nicotinonitrile: Synthesis, crystal structure, DFT and photophysical studies

In the current communication, we report the synthesis, spectroscopic, crystal structure, DFT and photophysical studies of a new nicotinonitrile derivative, viz. 2-methoxy-6-(4-methoxy-phenyl)-4-p-tolyl-nicotinonitrile (2) as a potential blue light emitting material. The compound 2 was synthesized in good yield via a simple route. The acquired spectral and elemental analysis data were in consistent with the chemical structure of 2. The single crystal study further confirms its three dimensional structure, molecular shape, and nature of short contacts. Its DFT calculations reveal that compound 2 possesses a non-planar structure and its theoretical IR spectral data are found to be in accordance with experimental values. In addition, its UV visible and fluorescence spectral measurements prove that the compound exhibits good absorption and fluorescence properties. Also, it shows positive solvatochromic effect when the solvent polarity was varied from non-polar to polar. (c) 2014 Elsevier B.V. All rights reserved.

Effect of quantum nuclear motion on hydrogen bonding

This work considers how the properties of hydrogen bonded complexes, X-H center dot center dot center dot Y, are modified by the quantum motion of the shared proton. Using a simple two-diabatic state model Hamiltonian, the analysis of the symmetric case, where the donor (X) and acceptor (Y) have the same proton affinity, is carried out. For quantitative comparisons, a parametrization specific to the O-H center dot center dot center dot O complexes is used. The vibrational energy levels of the one-dimensional ground state adiabatic potential of the model are used to make quantitative comparisons with a vast body of condensed phase data, spanning a donor-acceptor separation (R) range of about 2.4-3.0 angstrom, i.e., from strong to weak hydrogen bonds. The position of the proton (which determines the X-H bond length) and its longitudinal vibrational frequency, along with the isotope effects in both are described quantitatively. An analysis of the secondary geometric isotope effect, using a simple extension of the two-state model, yields an improved agreement of the predicted variation with R of frequency isotope effects. The role of bending modes is also considered: their quantum effects compete with those of the stretching mode for weak to moderate H-bond strengths. In spite of the economy in the parametrization of the model used, it offers key insights into the defining features of H-bonds, and semi-quantitatively captures several trends. (C) 2014 AIP Publishing LLC.

Effect of High-Pressure Torsion on Texture, Microstructure, and Raman Spectroscopy: Case Study of Fe- and Te-Substituted CoSb3

Fe0.05Co0.95Sb2.875Te0.125, a double-element-substituted skutterudite, was prepared by induction melting, annealing, and hot pressing (HP). The hot-pressed sample was subjected to high-pressure torsion (HPT) with 4 GPa pressure at 673 K. X-ray diffraction was performed before and after HPT processing of the sample; the skutterudite phase was observed as a main phase, but an additional impurity phase (CoSb2) was observed in the HPT-processed sample. Surface morphology was determined by high-resolution scanning electron microscopy. In the HP sample, coarse grains with sizes in the range of approximately 100 nm to 300 nm were obtained. They changed to fine grains with a reduction in grain size to 75 nm to 125 nm after HPT due to severe plastic deformation. Crystallographic texture, as measured by x-ray diffraction, indicated strengthening of (112), (102) poles and weakening of the (123) pole of the HPT-processed sample. Raman-active vibrational modes showed a peak position shift towards the lower energy side, indicating softening of the modes after HPT. The distortion of the rectangular Sb-Sb rings leads to broadening of Sb-Sb vibrational modes due to local strain fluctuation. In the HPT process, a significant effect on the shorter Sb-Sb bond was observed as compared with the longer Sb-Sb bond.

Effect of inductive effect on the formation of cocrystals and eutectics

There is a growing need to understand the factors that control the formation of different yet related multicomponent adducts such as cocrystals, solid solutions and eutectics from both fundamental and application perspectives. Benzoic acid and its structural analogues, having gradation in inductive force strengths, are found to serve as excellent coformers to comprehend the formation of above adducts with the antiprotozoal drug ornidazole. The combination of the drug with para-amino and -hydroxybenzoic acids resulted in cocrystals in accordance with the induction strength complementarity between the participant hydrogen bond donor-acceptor groups. The lack of adequate inductive forces for combinations with benzoic acid and other coformers was exploited to make eutectics of the drug. The isomorphous/isostructural relationship between para-amino and -hydroxybenzoic acid-drug cocrystals was utilized to make solid solutions, i.e. solid solutions of cocrystals. All in all, we successfully steered and expanded the supramolecular solid-form space of ornidazole.

Glycosidic bond hydrolysis in septanosides: a comparison of mono-, di-, and 2-chloro-2-deoxy-septanosides

A kinetic study of the hydrolytic stabilities of mono-, di-, and 2-chloro-2-deoxy septanosides, under acid-catalysis, is reported herein. A comparison of mono-and diseptanosides, shows that the glycosidic bond in the disaccharide is more stable than the monosaccharide. Further the glycosidic bond at the reducing end hydrolyzes almost twice as faster than that of the non-reducing end of the disaccharide. 2-Chloro-2-deoxy septanoside is found to be the most stable and its glycosidic bond hydrolysis occurs at elevated temperatures only. The orientation of the exo-cyclic hydroxymethyl group and the inductive effect are suggested to play a role in the rates of hydrolysis. (C) 2014 Elsevier Ltd. All rights reserved.

An encaged sigma* orbital in 3-methoxy-2,4,10-trioxaadamantane. Preferred exo-anomeric effect as revealed by the crystal structure

In the titled tricyclic orthocarbonate derivative, the three endocyclic C-O bonds are longer than the exo-cyclic C-O bond (similar to 4.40 angstrom vs. similar to 1.37 angstrom). This indicates an anomeric-type interaction between the two electron lone pairs on the exocyclic oxygen atom and the antibonding orbitals of the two antiperiplanar endocyclic C-O bonds. The remaining endocyclic C-O bond - marginally shorter than the other two apparently adds to this effect. Intriguingly, the antibonding orbital of the exocyclic C-O bond extends into the interior of the adamantyl cage, and is stereoelectronically prevented from overlapping with any of the six adjacent lone pairs. The results also seem to indicate a preference for interaction between a single donor oxygen atom and multiple acceptor antibonding orbitals rather than vice versa. The results add insightfully to the substantial body of evidence favouring the antiperiplanar lone pair hypothesis (ALPH). (C) 2014 Elsevier B.V. All rights reserved.

Al3+-Ion-Triggered Conformational Isomerization of a Rhodamine B Derivative Evidenced by a Fluorescence Signal - A Crystallographic Proof

A newly designed rhodamine B anisaldehyde hydrazone exhibits Al3+-ion-induced cis (L) to trans (L) conformational isomerization with respect to the xanthene moiety through a rotation about a N-N bond; the isomerization is indicated by a detectable naked-eye color change and a turn-on red fluorescence in 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) buffer (EtOH/Water 1:9 v/v; pH 7.4) at 25 degrees C. In support of this observation, detailed spectroscopic and physicochemical studies along with density function theory (DFT) calculations have been performed. This cis-to-trans conformational isomerization is due to Al3+ ion coordination, which induces this visual color change and the turn-on fluorescence response. To strengthen our knowledge of the conformational isomerization, detailed structural characterizations of the cis and trans isomers in the solid state were performed by single-crystal X-ray diffraction. To the best of our knowledge, this is the first structural report of both cis and trans conformational isomers for this family of compounds. Moreover, this noncytotoxic probe could be used to image the accumulation of Al3+ ions in HeLa and MCF-7 cell lines.

Three centered hydrogen bonds of the type C=O...H(N)...X-C in diphenyloxamide derivatives involving halogens and a rotating CF3 group: NMR, QTAIM, NCI and NBO studies

The existence of three centered C=O...H(N)...X-C hydrogen bonds (H-bonds) involving organic fluorine and other halogens in diphenyloxamide derivatives has been explored by NMR spectroscopy and quantum theoretical studies. The three centered H-bond with the participation of a rotating CF3 group and the F...H-N intramolecular hydrogen bonds, a rare observation of its kind in organofluorine compounds, has been detected. It is also unambiguously established by a number of one and two dimensional NMR experiments, such as temperature perturbation, solvent titration, N-15-H-1 HSQC, and F-19-H-1 HOESY, and is also confirmed by theoretical calculations, such as quantum theory of atoms in molecules (QTAIM), natural bond orbital (NBO) and non-covalent interaction (NCI).

Effect of compositional variations on the optical properties of SbxSe60-xS40 thin films

Thin films of SbxSe60-xS40( x= 10, 20, 30, and 40) were deposited by thermal evaporation from the prepared bulk materials on glass substrates held at room temperature. The film compositions were confirmed by using energy dispersive X-ray spectroscopy. X-ray diffraction studies revealed that all the as- deposited films have amorphous structure. The optical constants ( n, k, E-g, E-e, B-1/2) of the films were determined from optical transmittance data, in the spectral range 500-1200 nm, using the Swanepoel method. An analysis of the optical absorption spectra revealed an Urbach's tail in the low absorption region, while in the high absorption region an indirect band gap characterizes the films with different compositions. It was found that the optical band gap energy decreases as the Sb content increases. Finally, in terms of the chemical bond approach, degree of disorderness has been applied to interpret the decrease in the optical gap with increasing Sb content in SbxSe60-xS40 thin films. The changes in X-ray photo electron spectra and Raman shift in the films show compositional dependence. (C) 2015 Elsevier B.V. All rights reserved.

Intramolecular hydrogen bonds involving organic fluorine in the derivatives of hydrazides: an NMR investigation substantiated by DFT based theoretical calculations

The rare examples of intramolecular hydrogen bonds (HB) of the type the N-H center dot center dot center dot F-C, detected in a low polarity solvent in the derivatives of hydrazides, by utilizing one and two-dimensional solution state multinuclear NMR techniques, are reported. The observation of through-space couplings, such as, (1h)J(FH), and (1h)J(FN), provides direct evidence for the existence of intra-molecular HB. Solvent induced perturbations and the variable temperature NMR experiments unambiguously establish the presence of intramolecular HB. The existence of multiple conformers in some of the investigated molecules is also revealed by two dimensional HOESY and N-15-H-1 HSQC experiments. The H-1 DOSY experimental results discard any possibility of self or cross dimerization of the molecules. The derived NMR experimental results are further substantiated by Density Function Theory (DFT) based Non Covalent Interaction (NCI), and Quantum Theory of Atom in Molecule (QTAIM) calculations. The NCI calculations served as a very sensitive tool for detection of non-covalent interactions and also confirm the presence of bifurcated HBs.

Effect of laser irradiation on the optical properties of As40Sb15Se45 chalcogenide thin films

The exposure with band gap light of thermally evaporated As40Sb15Se45 amorphous film of 800 nm thickness, were found to be accompanied by optical changes. The as-prepared and illuminated thin films were studied by X-ray diffraction, Fourier Transform Infrared Spectroscopy and X-ray Photoelectron Spectroscopy and Raman spectroscopy. The optical band gap was reduced due to photo induced effects along with the increase in disorder. These optical properties changes are due to the change of homopolar bond densities. The core level peak shifting in XPS spectra and Raman shift supports the optical changes happening in the film due to light exposure.

Isotopic fractionation in proteins as a measure of hydrogen bond length

If a deuterated molecule containing strong intramolecular hydrogen bonds is placed in a hydrogenated solvent, it may preferentially exchange deuterium for hydrogen. This preference is due to the difference between the vibrational zero-point energy for hydrogen and deuterium. It is found that the associated fractionation factor (I) is correlated with the strength of the intramolecular hydrogen bonds. This correlation has been used to determine the length of the H-bonds (donor-acceptor separation) in a diverse range of enzymes and has been argued to support the existence of short low-barrier H-bonds. Starting with a potential energy surface based on a simple diabatic state model for H-bonds, we calculate (I) as a function of the proton donor-acceptor distance R. For numerical results, we use a parameterization of the model for symmetric 0-H. ``.0 bonds R. H. McKenzie, Chem. Phys. Lett. 535, 196 (2012)]. We consider the relative contributions of the 0-H stretch vibration, O-H bend vibrations (both in plane and out of plane), tunneling splitting effects at finite temperature, and the secondary geometric isotope effect. We compare our total (I) as a function of R with NMR experimental results for enzymes, and in particular with an earlier model parametrization (D(R), used previously to determine bond lengths. (C) 2015 AIP Publishing LLC.

Effect of Chalcogens on Electronic and Photophysical Properties of Vinylene-Based Diketopyrrolopyrrole Copolymers

Three vinylene linked diketopyrrolopyrrole based donor acceptor (D-A) copolymers have been synthesized with phenyl, thienyl, and selenyl units as donors. Optical and electronic properties were investigated with UV-vis absorption spectroscopy, cyclic voltammetry, near edge X-ray absorption spectroscopy, organic field effect transistor (OFET) measurements, and density functional theory (DFT) calculations. Optical and electrochemical band gaps decrease in the order phenyl, thienyl, and selenyl. Only phenyl-based polymers are nonplanar, but the main contributor to the larger band gap is electronic, not structural effects. Thienyl and selenyl polymers exhibit ambipolar charge transport but with higher hole than electron mobility. Experimental and theoretical results predict the selenyl system to have the best transport properties, but OFET measurements prove the thienyl system to be superior with p-channel mobility as high as 0.1 cm(2) V-1 s(-1).

Ru (II)-Catalyzed C-H Activation: Ketone-Directed Novel 1,4-Addition of Ortho C-H Bond to Maleimides

A 1,4-addition with the nucleophilic center generated at the ortho carbon atom of an aromatic ketone in the presence of the highly reactive alpha-C-H bond, using a directing group strategy, is presented. The reaction yields pharmaceutically useful 3-arylated succinimide derivatives. In order to gain understanding of this redox neutral reaction, despite the presence of copper acetate, and to substantiate the lack of Heck-type products, DFT calculations have been carried out.