Joint Experimental and Theoretical Analysis of Order Disorder Effects in Cubic BaZrO(3) Assembled Nanoparticles under Decaoctahedral Shape

Periodic first-principles calculations based on density functional theory at the B3LYP level has been carried out to investigate the photoluminescence (PL) emission of BaZrO(3) assembled nanoparticles at room temperature. The defect created in the nanocrystals and their resultant electronic features lead to a diversification of electronic recombination within the BaZrO(3) band gap. Its optical phenomena are discussed in the light of photoluminescence emission at the green-yellow region around 570 nm. The theoretical model for displaced atoms and/or angular changes leads to the breaking of the local symmetry, which is based on the refined structure provided by Rietveld methodology. For each situation a band structure, charge mapping, and density of states were built and analyzed. X-ray diffraction (XRD) patterns, UV-vis measurements, and field emission scanning electron microscopy (FE-SEM) images are essential for a full evaluation of the crystal structure and morphology.

Experimental and theoretical investigation of first hyperpolarizability in aminophenols

This work reports theoretical and experimental studies on the first hyperpolarizability (beta) of aminophenols, evaluating the influence of the NH(2) group position relative to the OH group on the hyperpolarizability. A new extension of hyper-Rayleigh scattering technique using picosecond pulse trains was employed to obtain the experimental absolute values of (beta). The theoretical static beta(0) values were calculated using AMI method implemented in the AMPAC program. The theoretical and experimental data show a clear dependence between beta and the relative position of the electron donor (D) and acceptor (A) groups, presenting the 2-aminophenol the higher values. Moreover, calculations show excellent qualitative agreement between theoretical and experimental data, which are improved when the simulations considering the solvated molecule in a combination of discrete solvent molecules interacting with the solute and the application of continuous dielectric model. Besides, the study indicates that the experimental hyperpolarizabilities seem to be a property of the solute-solvation shell system. These facts have affirmed that the theoretical approach employed can be successfully used to foresee the variation in beta due to modifications in the D/A position. Moreover, a theoretical study of the ground state absorption is performed and compared with experimental data. (C) 2008 Elsevier B.V. All rights reserved.

Structural effects and hydrogen bonds on N,N `-di(methoxycarbonylsulfenyl)urea, [CH(3)OC(O)SNH](2)CO, studied by experimental and theoretical methods

Pure N,N`-di(methoxycarbonylsulfenyl)urea, [CH(3)OC(O)SNH](2)CO, is quantitatively prepared by the hydrolysis reaction of CH(3)OC(O)SNCO and characterized by (1)H NMR, GC-MS and FTIR spectroscopy techniques. Structural and conformational properties are analyzed using a combined approach with data obtained from X-ray diffraction, vibrational spectra and theoretical calculation methods. The IR and Raman spectra for normal and deuterated species are reported. The crystal structure of [CH(3)OC(O)SNH](2)CO was determined by X-ray diffraction methods. The substance crystallizes in the orthorhombic P2(1)2(1)2 space group with a = 9.524(2), b = 12.003(1), c = 4.481 (1) angstrom, and Z = 2 moieties in the unit cell. The molecule is sited on a twofold crystallographic axis (C(2)) parallel to c and shows the anti-anti conformation (S-N single bonds antiperiplanar with respect to the opposite C-N single bonds in sulfenyl-urea-sic group). Neighboring molecules are arranged in a chain motif that extends along the C(2)-axis and is held by bifurcated NH center dot center dot center dot O center dot center dot center dot HN intermolecular bonds. A local planar symmetry is observed in the crystal for the central -SN(H)C(O)N(H)S- skeleton. Experimental and calculated data allow to trace this structural feature to the occurrence of N-H center dot center dot center dot O=C hydrogen bonding interactions. Calculated vibrational and structural properties are in good agreement with the experimentally determined features. (C) 2008 Elsevier B.V. All rights reserved.

Cyclocreatine, an anticancer and neuroprotective agent. Spectroscopic, structural and theoretical study

The structural, spectroscopic and theoretical study of cyclocreatine (1-carboxymethyl-2-iminoimidazolidine, CyCre) has been performed prompted by the biological relevance of the molecule and its potential role as a ligand in biometalic compounds. The crystal structure of CyCre has been determined by X-ray diffraction methods. The compound crystallizes as a zwitterion in the monoclinic system, space group P2(1)/c. The crystal is further stabilized by a network of N-H center dot center dot center dot O bonds. Infrared and Raman spectra of the solid, electronic spectra of aqueous solutions at different pH values and (1)H and (13)C NMR spectra have been recorded and analyzed. Band assignments were accomplished with the help of theoretical calculations. Optimized molecular geometries, harmonic vibrational frequencies and molecular electrostatic potentials were calculated using methods based on the density functional theory. (C) 2010 Elsevier B.V. All rights reserved.

Experimental and theoretical investigation of molecular structure and conformation of the 4-isopropylthioxanthone

In this study, the molecular structure and conformational analyses of the 4-isopropylthioxanthone (4-ITX) are reported according to experimental and theoretical results. The compound crystallizes in the centrosymmetric P (1) over bar space group with only one molecule in the asymmetric unit, presenting the most stable conformation, in which the three fused-rings adopt a planar geometry, and the isopropyl group assumes a torsional angle with less sterical hindrance. The structural and conformational analyses were performed using theoretical calculations such as Hartree-Fock (HF), DFT method in combination with 6-311G(d,p) and 6-31++G(d,p) and the results were compared with infrared spectroscopy (FT-IR) and X-ray diffraction (XRD). The supramolecular assembly of 4-ITX is kept by non-classical C-H center dot center dot center dot O hydrogen bonds and weak interactions such as pi-pi stacking. 4-ITX was also studied by (1)H and (13)C NMR spectroscopy. UV-Vis absorption spectroscopic properties of the 4-ITX showed the long-wavelength maximum shifts towards high energy when the solvent polarity increases. (C) 2011 Elsevier B.V. All rights reserved.

Spectroscopic and theoretical studies of some N-methoxy-N-methyl-2-[(4 `-substituted) phenylsulfonyl]propanamides

The analysis of the IR carbonyl band of the N-methoxy-N-methyl-2-[(4`-substituted)phenyisulfonyI]propanamides Y-PhSO(2)CH(Me)C(O)N(OMe)Me (Y = OMe 1, Me 2, H 3, Cl 4, NO(2) 5), supported by HF/6-31G(d,p) calculations of 3,, indicated the existence of two gauche conformers (g(1) and g(2)), the g, conformer being the most stable and the least polar one (in gas phase and in solution). Both conformers are present in solution of the non polar solvent (CCl(4)) for 1-5 and in solution of the more polar solvents (CHCl(3)) for 1. 4, 5 and (CH(2)Cl(2)) for 5, while only the g(1) conformer is present in solution of the most polar solvent (CH(3)CN) for 1-5. The g, and g2 conformers correspond to the enantiomeric pairs of diastereomers (diast(1) and diast(2)) whose relative configurations are [C(3)(R)N(R)]/[C(3)(s)N(s)] and [C(3)(R)N(s)]/[C(3)(s)N(R)], respectively. The computed carbonyl frequencies for g(1) (diast(1)) and g(2) (diast(2)) stereoisomers of3 match well the experimental values. The NBO analysis, for 3 shows the important role of the orbital interactions in conformer stabilization and the overall balance of these interactions corroborates that the g, conformer is more stable than the 92 one. The observed abnormal solvent effect on the relative intensities of the carbonyl doublet components is attributed to the molecular crowding in the g2 conformer which hinders its solvation in comparison to the g, conformer (diast(1)). X-ray single crystal analysis performed for 3 shows the existence Of two 92, and g(1b) conformers of diastereomers (diast2, and diast(1b)) whose absolute configurations are [C(3)(R)N(s)] and [C(3)(R)N(R)], respectively. The larger population and. thus, the larger stabilization of the g(2), conformer over the gib form in the crystals may be associated with a larger energy gain deriving from dipole moment coupling in the former conformer along with a series of C-H center dot center dot center dot O electrostatic and hydrogen bond interactions, (C) 2009 Elsevier B.V. All rights reserved.

Spectroscopic and theoretical studies of some N-methoxy-N-methyl-2-[(4 `-substituted) phenylthio]propanamides

The analysis of the IR carbonyl band of the N-methoxy-N-methyl-2-[(4`-substituted)phenylthio]propanamides Y-PhSCH(Me)C(O)N(OMe)Me (Y=OMe 1, Me 2, H 3, Cl 4, NO(2) 5), supported by B3LYP/cc-pVDZ calculations of 3, indicated the existence of two gauche conformers (g(1) and g(2)), the g(1) conformer being the more stable and the less polar one (in gas phase and in solution). Both conformers are present in solution of the polar solvents (CH(2)Cl(2) and CH(3)CN) for 1-5 and in solution of the less polar solvent (CHCl(3)) for 1-4, while only the g(1) conformer is present in solution of non polar solvents (n-C(6)H(14) and CCl(4)) and in solution of CHCl(3) for 5. NBO analysis shows that both the sigma(C-S) -> pi*(C=O) (hyperconjugative) and the pi(C=O) -> sigma*(C-S) orbital interactions contribute almost to the same extent for the stabilization of g(1) and g(2) conformers. The pi*(C=O) -> sigma*(C-S), n(S) -> pi*(C=O) and the n(S) -> pi*(C=O) orbital interactions stabilize more the g(1) conformer than the g(2) one. Moreover, the suitable geometry of the g(1) conformer leads to its stabilization through the LP(O2) -> sigma*(C8-H11) orbital interaction (hydrogen bond) along with the strong O([CO])(delta-) center dot center dot center dot H([O-Ph])(delta+) electrostatic interaction. On the other hand, the appropriate geometry of the g(2) conformer leads to its stabilization by the LP(O22) -> sigma*(C9-H13) orbital interaction (hydrogen bond) along with the weak O([OMe])(delta-) center dot center dot center dot H([o`-Ph])(delta+) electrostatic static interaction. As for the 4`-nitro derivative 5 the ortho-phenyl hydrogen atom becomes more acidic, leading to a stronger O([CO])(delta-) center dot center dot center dot H([o-Ph])(delta+) interaction and, thus, into a larger stabilization of the g(1) conformer in the whole series. This trend is responsible for the unique IR carbonyl band in CHCl(3) solution of 5. The larger occupancy of the pi*(C=O) orbital of the g(1) conformer relative to that of the g(2) conformer, along with the O([CO])(delta-) center dot center dot center dot H([o-Ph])(delta+) electrostatic interaction (hydrogen bond) justifies the lower carbonyl frequency of the g(1) conformer with respect to the g(2) one, in gas phase and in solution. (C) 2008 Elsevier B.V. All rights reserved.

Spectroscopic and theoretical studies of some N,N-diethyl-2-[(4 `-substituted)phenylsulfonyl]acetamides

The analysis of the IR carbonyl band of the N,N-diethyl-2-[(4`-substituted)phenylsulfonyl]acetamides Et(2)NC(O)CH(2)S(O)(2)-C(6)H(4)-Y (Y = OMe 1, Me 2,1-13, Cl 4, Br 5, NO(2) 6) supported by B3LYP/6-31G(d,p) calculations for 3, indicated the existence of three pairs (anti and syn) of cis (c) and gauche (g(1) and g(2)) conformers in the gas phase, being the gauche conformers significantly more stable than the cis ones. The anti geometry is more stable than the syn one, for each pair of cis and gauche conformers. The summing up of the orbital (NBO analysis) and electrostatic interactions justifies quite well the populations and the v(CO) frequencies of the anti and syn pairs of c, g(1) and g(2) conformers. The IR higher carbonyl frequency component whose population is ca. 10%, in CCl(4), may be ascribed to the least stable and most polar cis conformer pair (in the gas phase) and the lower frequency component whose population is ca. 90%, to the summing up of the populations of the two most stable and least polar gauche conformer pairs (g(1) and g(2)) (in the gas phase). The reversal of the cis(c)/gauche (g(1) + g(2)) population ratio observed in chloroform ca. 60% (cis)/40% (gauche) and the occurrence of the most polar cis(c) conformer only, in acetonitrile, strongly suggests the coalescence of the two gauche components in a unique carbonyl band in solution. A further support to this rationalization is given by the single point PCM solvation model performed by HF/6-31G(d,p) method, which showed a progressive increase of the c/(g(1) + g(2)) ratio going from gas to CCl(4), to CHCl(3) and to CH(3)CN. X-ray single crystal analysis of 4 indicates that this compound assumes, in the solid state, the syn-clinal (gauche) conformation with respect to the [O=C-CH(2)-S] moiety, and the most stable anti geometry relative to the [C(O)N(CH(2)CH(3))(2)] fragment. In order to obtain larger energy gain from the crystal packing the molecules of 4 are linked in centrosymmetric dimers through two C-H center dot center dot center dot O interactions (C-H([O-Ph])center dot center dot center dot O([SO2])) forming a step ladder. (C) 2011 Elsevier B.V. All rights reserved.

Spectroscopic and theoretical studies of some 2-ethylsulfinyl-(4 `-substituted)-phenylthioacetates

The analysis of the IR nu(co) bands of the 2-ethylsulfinyl-(4`-substituted)-phenylthioacetates 4`-Y-C(6)H(4)SC(O)CH(2)S(O)Et (Y = NO(2) 1, Cl 2, Br 3, H 4, Me 5, OMe 6) supported by B3LY/6-31G(d,p) calculations along with the NBO analysis for 1.4 and 6 and X-ray analysis for 3, indicated the existence of four gauche (q-g-syn, g(3)-syn. g(1)-atin and q-g(2)-syn) conformers for 1-6 The calculations reproduce quite well the experimental results, i e the computed q-g-syn and g3-syn conformers correspond in the IR spectrum (in solution), to the nu(co) doublet higher frequency component of larger intensity, while the computed grant, conformer correspond to the nu(co) doublet lower frequency component (in solution) NBO analysis showed that the n(s) -> pi(center dot)(c1=o2), no(co) -> sigma(c1-s3), no(co) -> sigma(c1-c4) orbital interactions are the main factors which stabilize the q-g-syn, g(3)-syn, g(1)-anti and q-g(2)-syn conformers for 1, 4 and 6 The no(co) -> sigma(c1-s3) interaction which stabilizes the q-g-syn, g(3)-syn and q-g(2)-syn conformers into a larger extent than the granti conformer, is responsible for the larger tto frequencies of the former conformers relative to the latter one. The q-g-syn, g(3)-syn and q-g(2)-syn conformers are further stabilized sigma(c4-s5) -> pi(co)center dot (strong). pi(co)/sigma(c1-c4,) no(co) -> sigma(c6-H17[Et]) (weak) and pi(co)/sigma(c4-c5) pi(co) (strong) orbital interactions. The q-g-syn conformer is also stabilized by sigma(c4-s5) -> pi(center dot)(co) (strong), pi(co)/sigma(c4-c5).no(co) -> sigma(c6-H17[Et]), pi(C9=C11[ph]) -> sigma(c4-H6x-CH2]) (weak). no((SO)) -> sigma(C11-H23[ph]) (medium) pi(co)/sigma(c4-c5)(strong) orbital interactions. The q-g-syn conformei is further stabilized by the n(S5) O((C))(8-) S((SO))(8+) attractive Coulornbic interaction while the q-g(2)-syn conformer is destabilized by the n55 0,8c-0) repulsive Coulombic interaction. This analysis indicates the following conformer stabilization order. q-g-syn, g(3)-syn > g(1)-anti >> q-g(2)-syn X-ray single crystal analysis of 3 indicates that it assumes in the solid a distorted q-g(2)-syn geometry which is stabilized through almost the same orbital and Coulombic interaction which takes place for the q-g(2)-syn conformer, in the gas, along with dipole moment coupling and a series intermolecular C-HO0 interactions. (C) 2010 Elsevier B V All rights reserved

Conformational preferences for some 2-substituted N-methoxy-N-methylacetamides through spectroscopic and theoretical studies

The analysis of the IR carbonyl band of the 2-substituted N-methoxy-N-methylacetamides Y-CH(2)C(O)-N(OMe)Me (Y = F1, OMe 2, OPh 3, Cl 4), supported by B3LYP/6-311++G(3df, 3pd) calculations along with the NBO analysis for 1-4, indicated the existence of cis-gauche conformers i.e. (c) and (g) for 1 and 3, (c(1), c(2)) and (g(1), g(2)) for 2, and (c) and (g(1), g(2)) for 4. In the gas phase, the g conformer population prevails over the c one, for 1 and 3, the (c(1) + c(2)) population prevails over the (g(1) + g(2)) one for 2, and the (g(1) + g(2)) conformer population is more abundant than (c) one for 4. In n-hexane solution, the cis conformer is more abundant for 1-3. The occurrence of Fermi resonance in the nu(CO) region, in n-hexane, precludes the estimative of relative populations of the (c, g(1), g(2)) conformers for 4. The SCI-PCM calculations agree with the solvent effect on the nu(CO) band component relative intensities for 1-3. NBO analysis showed that the n(N) -> pi.(CO), orbital interaction is the main factor which stabilizes the gauche (g, g(1), g(2)) conformers for 1-4 into a larger extent relative to the cis (c, c(1), c(2)) ones. The n(y) -> pi(.)(Co,) sigma(C-Y) -> pi.(CO,) pi(CO) -> sigma(C-Y) and 7co orbital interactions still contribute, but into a minor extent for the stabilization of the gauche conformers relative to the cis ones. The existence of some pyramidalization at the nitrogen atom of the Weinreb amides 1-4 is responsible for the occurrence of Y(delta)-(4)center dot center dot center dot O(delta)-(9) and Y(delta)-(4)center dot center dot center dot N(delta)-(7) short contacts in the gauche (g, g(1), g(2)) conformers, which originates strong repulsive Coulombic interactions, acting in opposition to the large orbital stabilization of the gauche conformer with respect to the cis one. Therefore, a delicate balance of the Coulombic and orbital interactions seems to be responsible for the observed stabilization of the gauche (g, g(1), g(2)) and cis (c, c(1), c(2)) conformers, both in the gas phase and in the solution for 1-4. However, the cis conformer predominance, in non polar solvents, for the 2-substituted N-methoxy-N-methyl acetamides 1-3, bearing in a first raw (fluorine and oxygen) atoms, is in the opposite direction to the gauche conformer preference for the corresponding 2-substituted N,N-dialkyl-acetamides. (C) 2010 Elsevier B.V. All rights reserved.

A combined X-ray and theoretical study of flavonoid compounds with anti-inflammatory activity

The structure of 7,4`-dimethoxy-3`-acetylflavone (tithonin-Ac) has been determined by X-ray diffraction and its geometry is compared with optimized geometrical parameters obtained by means of density functional theory at the B3LYP/6-311++G(d,p) level of calculation. in addition, vertical ionization potential (IPv) and acidity for tithonin-Ac and two derivatives have been also calculated. Calculations of spin densities were also performed for the radical formed by the electron abstraction of other flavones. The unpaired electron is located on C3 carbon atom (21-25%). (C) 2008 Elsevier B.V. All rights reserved.

Crystal structure and theoretical calculations of Julocrotine, a natural product with antileishmanial activity

Julocrotine, N-(2,6-dioxo-l-phenethyl-piperidin-3-yl)-2-methyl-butyramide, is a potent antiproliferative agent against the promastigote and amastigote forms of Leishmania amazonensis (L.). In this work, the crystal structure of Julocrotine was solved by X-ray diffraction, and its geometrical parameters were compared with theoretical calculations at the B3LYP and HF level of theory. IR and NMR spectra also have been obtained and compared with theoretical calculations. IR absorptions calculated with the B3LYP level of theory employed together with the 6-311G+(d,p) basis set, are close to those observed experimentally. Theoretical NMR calculations show little deviation from experimental results. The results show that the theory is in accordance with the experimental data. (C) 2007 Wiley Periodicals, Inc.

Iridium(III) N-heterocyclic carbene complexes: an experimental and theoretical study of structural, spectroscopic, electrochemical and electrogenerated chemiluminescence properties

Four cationic heteroleptic iridium(III) complexes have been prepared from methyl- or benzyl-substituted chelating imidazolylidene or benzimidazolylidene ligands using a Ag(I) transmetallation protocol. The synthesised iridium(III) complexes were characterised by elemental analysis, (1)H and (13)C NMR spectroscopy and the molecular structures for three complexes were determined by single crystal X-ray diffraction. A combined theoretical and experimental investigation into the spectroscopic and electrochemical properties of the series was performed in order to gain understanding into the factors influencing photoluminescence and electrochemiluminescence efficiency for these complexes, with the results compared with those of similar NHC complexes of iridium and ruthenium. The N^C coordination mode in these complexes is thought to stabilise thermally accessible non-emissive states relative to the case with analogous complexes with C^C coordinated NHC ligands, resulting in low quantum yields. As a result of this and the instability of the oxidised and reduced forms of the complexes, the electrogenerated chemiluminescence intensities for the compounds are also low, despite favourable energetics. These studies provide valuable insights into the factors that must be considered when designing new NHC-based luminescent complexes.

Toward an understanding of intermediate- and short-range defects in ZnO single crystals. A combined experimental and theoretical study

A joint use of experimental and theoretical techniques allows us to understand the key role of intermediate- and short-range defects in the structural and electronic properties of ZnO single crystals obtained by means of both conventional hydrothermal and microwave-hydrothermal synthesis methods. X-ray diffraction, Raman spectra, photoluminescence, scanning electronic and transmission electron microscopies were used to characterize the thermal properties, crystalline and optical features of the obtained nano and microwires ZnO structures. In addition, these properties were further investigated by means of two periodic models, crystalline and disordered ZnO wurtzite structure, and first principles calculations based on density functional theory at the B3LYP level. The theoretical results indicate that the key factor controlling the electronic behavior can be associated with a symmetry breaking process, creating localized electronic levels above the valence band.

A Joint Experimental and Theoretical Study on the Nanomorphology of CaWO4 Crystals

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)