Synthesis and characterization of the mer-[RuCl3(NO)(dppb)] isomer. X-ray structures of fac-[RuCl3(NO)(dppm)], cis-[RuCl2(dppm)2] and mer-[RuCl3(NO)(dppb)] [dppm=1,2-Bis(diphenylphosphino)methane and dppb=1,4-Bis(diphenylphosphino)butane]

The fac-[RuCl3(NO)(dppm)] (1) and cis-[RuCl2(dppm)2] (2) complexes were obtained with co-crystallization in the solid state from the reaction of RuCl3(NO) with the diphosphine in dichloromethane. mer-[RuCl3(NO)(dppb)] (3) was obtained from [RuCl3(dppb)(H2O)] by bubbling NO for 30 min in the same solvent. The crystal and molecular structures of these three compounds have been determined from X-ray studies. © Elsevier Science Ltd.

fac-[RuCl3(no)(dppb)] (I) and mer-[RuCl3(NO)(diop)] (II) complexes: Syntheses, characterization and x-ray structures

The fac-[RuCl3(NO)(dppb)] complex I has been prepared from solution of the correspondent mer isomer in refluxing methanol (dppb = 1,4-bis(diphenylphosphino)butane). The mer-[RuCl3(NO)(diop)] (II) has been obtained from the mer-[RuCl3(diop)(H2O)] by bubbling NO for 1 h in dichloromethane (diop = 2S,3S-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane). The complexes have been characterized by microanalysis, cyclic voltammetry (CV), IR and 31P{1H} NMR spectroscopies. The crystal and molecular structures of these two compounds have been determined from X-ray studies. The mer-[RuCl3(NO)(dppb)] isomer III was characterized in solution by NMR spectra (31P{1H}, 1H{31P}, 31P-1H HETCORR, COSY 1H-1H, HMQC 1H-13C and HMBC 1H-13C). © 2002 Elsevier Science Ltd. All rights reserved.

Structural refinement and photoluminescence properties of cube-like (Ca 1-xCu x)TiO 3 crystals synthesized by the microwave-hydrothermal method

In this work, (Ca 1-xCu x)TiO 3 crystals with (x = 0, 0.01 and 0.02), labeled as CTO, CCTO1 and CCTO2, were synthesized by the microwave-hydrothermal method at 140°C for 32 min. XRD patterns (Fig. 1), Rietveld refinement and FT-Raman spectroscopy indicated that these crystals present orthorhombic structure Pbnm. Micro-Raman and XANES spectra suggested that the substitution of Ca by Cu in A-site promoted a displacement of the [TiO6]-[TiO6] clusters adjacent from its symmetric center, which leads distortions on the [CaO 12] clusters neighboring and consequently cause the strains into the CaTiO3 lattice. FE-SEM images showed that these crystals have an irregular shape as cube like probably indicating an Ostwald-ripening and self-assemble as dominant mechanisms to crystals growth. The powders presented an intense PL blue-emission.

Characterization, and crystal structure of thiophenyl-2-methylidene-2- aminophenol

The Schiff base thiophenyl-2-methylidene-2-aminophenol (ImineOH) is obtained from a stoichiometric mixture of 2-thiophenecarboxaldehyde and 2-aminophenol in ethanol under reflux at 90 C. Its crystal structure is determined by single crystal X-ray diffraction. ImineOH packs in an orthorhombic unit cell in the Pbca space group with the unit cell parameters a = 16.942(4) Å, b = 13.4395(11) Å, and c = 17.5857(12) Å, V = 4004.1(10) Å3, Z = 16. Strong hydrogen bonds are present in the ImineOH structure. Apart from the X-ray study, ImineOH was characterized by elemental analysis (CHN-S) and FT-IR (4000 cm-1 to 400 cm-1), UV-Vis and 13C, 1H, and 15N NMR spectroscopic measurements. © 2013 Pleiades Publishing, Ltd.

Isolation, X-ray crystal structure and theoretical calculations of the new compound 8-Eepicordatin and identification of others terpenes and steroids from the bark and leaves of Croton palanostigma Klotzsch

Estudos fitoquímicos com as cascas do caule e com as folhas de Croton palanostigma Klotzsch (Euphorbiaceae) levaram ao isolamento do novo diterpeno clerodânico 8-epicordatina (2), além de éster metílico do ácido 12-oxohardwickiico (3), aparisthmano, cordatina (1), ácido ent-trachiloban-18-óico, óxido de ent-13-epimanoila, óxido de ent-3-oxo-13-epimanoila, óxido de ent-3β-hidroxi-13-epimanoila, sitosterol, estigmasterol, estigmastan-3-ona, 6β-hidroxiestigmast-4-en-3-ona, 6β-hidroxiestigmasta-4,22-dien-3-ona, estigmast-4-en-3-ona, estigmasta-4,22-dien-3-ona, ácido 3-O-acetilaleuritolico, 11α-hidroxiurs-12-en-3-ona, α-amirenona, 24-metilenocicloartenona e lupenona. Estas substâncias foram isoladas através de procedimentos fitoquímicos usuais e suas estruturas foram deduzidas por estudos espectroscópicos, incluindo experimentos em 2D. Adicionalmente, a estrutura cristalina de 8-epicordatina (2) foi determinada por difração de raios-X. Cálculos teóricos de RMN ao nível B3PW91/DGDZVP foram usados para confirmação dos assinalamentos dos deslocamentos químicos dos hidrogênios H-7α e H-7β de 8-epicordatina.

Protonation Pattern, Tautomerism, Conformerism, and Physicochemical Analysis in New Crystal Forms of the Antibiotic Doxycycline

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

A theoretical investigation of the structural and eletronic properties of orthorhombic CaZrO3

A CaZrO3 (CZO) powder was prepared by the soft chemical, polymeric precursor method (PPM). The CZO crystalline structure was investigated by powder X-ray diffraction (XDR), Retvield Refinament data, Raman spectra and ultraviolet–visible absorption spectroscopy. A theoretical study was performed using a periodic quantum mechanical calculation (CRYSTAL09 program). The periodic model built for the crystalline CZO structure was consistent with the experimental data obtained from structural and electronic properties. These results show that the material has an orthorhombic structure with experimental and theoretical gap values of 5.7 eV and 6.2 eV, respectively. In this article, we discuss the hybridization process of the oxygen p-orbitals and of the zirconium d-orbitals and analyze their band structures and density of states (partial and total).

Ellipsometric Study of Single-Crystal γ-Inse From 1.5 To 9.2 Ev

We report the component E ┴ c of the pseudodielectric-function tensor <ε(E)> = <ε1(E)> + i< ε2(E)> of γ-phase single-crystal InSe, obtained from 1.5 to 9.2 eV by vacuum-ultraviolet spectroscopic ellipsometry with the sample at room temperature. Overlayer artifacts were reduced as far as possible by measuring fresh surfaces prepared by cleavage. Accurate critical-point energies of observed structures were obtained by a combined method of spectral analysis.

Polymorphic-induced transformations in CaTa2O6 single-crystal fibers obtained by laser-heated pedestal growth

Calcium tantalite (CaTa2O6) single crystal fibers were obtained by the laser-heated pedestal growth method (LHPG). At room temperature, this material can present three polymorphic modifications. The rapid crystallization inherent to the LHPG method produced samples within the Pm3 space group, with some chemical disorder. In order to check for polymorphic-induced transformations, the CaTa2O6 fibers have been submitted to different thermal treatments and investigated by micro-Raman spectroscopy. For short annealing times (15 min) at 1200 °C, the cubic modification was maintained, though with an improved crystalline quality, as evidenced by the enhanced inelastic scattered intensity (by ca. 250%) and narrowing of Raman bands. The polarized Raman spectra respected very well the predicted symmetries and the selection rules for this cubic modification. On the other hand, long annealing times (24 h) at 1200 °C led to a complete (irreversible) polymorphic transformation. The Raman bands became still more intense (ca. 15 times larger than for the as-grown fibers), narrower, and several new modes appeared. Also, the spectra became unpolarized, demonstrating a polycrystalline nature of the transformed crystals. The observed Raman modes could be fully assigned to an orthorhombic modification of CaTa2O6 belonging to the Pnma space group.

Studies of Inorganic Layer and Framework Structures Using Time-, Temperature- and Pressure-Resolved Powder Diffraction Techniques

This thesis is concerned with in-situ time-, temperature- and pressure-resolved synchrotron X-ray powder diffraction investigations of a variety of inorganic compounds with twodimensional layer structures and three-dimensional framework structures. In particular, phase stability, reaction kinetics, thermal expansion and compressibility at non-ambient conditions has been studied for 1) Phosphates with composition MIV(HPO4)2·nH2O (MIV = Ti, Zr); 2) Pyrophosphates and pyrovanadates with composition MIVX2O7 (MIV = Ti, Zr and X = P, V); 3) Molybdates with composition ZrMo2O8. The results are compiled in seven published papers and two manuscripts. Reaction kinetics for the hydrothermal synthesis of α-Ti(HPO4)2·H2O and intercalation of alkane diamines in α-Zr(HPO4)2·H2O was studied using time-resolved experiments. In the high-temperature transformation of γ-Ti(PO4)(H2PO4)·2H2O to TiP2O7 three intermediate phases, γ'-Ti(PO4)(H2PO4)·(2-x)H2O, β-Ti(PO4)(H2PO4) and Ti(PO4)(H2P2O7)0.5 were found to crystallise at 323, 373 and 748 K, respectively. A new tetragonal three-dimensional phosphate phase called τ-Zr(HPO4)2 was prepared, and subsequently its structure was determined and refined using the Rietveld method. In the high-temperature transformation from τ-Zr(HPO4)2 to cubic α-ZrP2O7 two new orthorhombic intermediate phases were found. The first intermediate phase, ρ-Zr(HPO4)2, forms at 598 K, and the second phase, β-ZrP2O7, at 688 K. Their respective structures were solved using direct methods and refined using the Rietveld method. In-situ high-pressure studies of τ-Zr(HPO4)2 revealed two new phases, tetragonal ν-Zr(HPO4)2 and orthorhombic ω-Zr(HPO4)2 that crystallise at 1.1 and 8.2 GPa. The structure of ν-Zr(HPO4)2 was solved and refined using the Rietveld method. The high-pressure properties of the pyrophosphates ZrP2O7 and TiP2O7, and the pyrovanadate ZrV2O7 were studied up to 40 GPa. Both pyrophosphates display smooth compression up to the highest pressures, while ZrV2O7 has a phase transformation at 1.38 GPa from cubic to pseudo-tetragonal β-ZrV2O7 and becomes X-ray amorphous at pressures above 4 GPa. In-situ high-pressure studies of trigonal α-ZrMo2O8 revealed the existence of two new phases, monoclinic δ-ZrMo2O8 and triclinic ε-ZrMo2O8 that crystallises at 1.1 and 2.5 GPa, respectively. The structure of δ-ZrMo2O8 was solved by direct methods and refined using the Rietveld method.

Liquid crystal polymers: macromolecular design for enhanced performances

During this work, done mainly in the laboratories of the department of Industrial Chemistry and Materials of the University of Bologna but also in the laboratories of the Carnegie Mellon University in collaboration with prof. K. Matyjaszewski and at the university of Zaragoza in collaboration with prof. J. Barberá, was focused mainly on the synthesis and characterization of new functional polymeric materials. In the past years our group gained a deep knowledge about the photomodulation of azobenzene containing polymers. The aim of this thesis is to push forward the performances of these materials by the synthesis of well defined materials, in which, by a precise control over the macromolecular structures, better or even new functionality can be delivered to the synthesized material. For this purpose, besides the rich photochemistry of azoaromatic polymers that brings to the application, the control offered from the recent techniques of controlled radical polymerization, ATRP over all, gives an enormous range of opportunity for the developing of a new generation of functional materials whose properties are determinate not only by the chemical nature of the functional center (e.g. azoaromatic chromophore) but are tuned and even amplified by a synergy with the whole macromolecular structure. Old materials in new structures. In this contest the work of this thesis was focused mainly on the synthesis and characterization of well defined azoaromatic polymers in order to establish, for the first time, precise structure-properties correlation. In fact a series of well defined different azopolymers, chiral and achiral, with different molecular weight and highly monodisperse were synthesized and their properties were studied, in terms of photoexpansion and photomodulation of chirality. We were then able to study the influence of the macromolecular structure in terms of molecular weight and ramification on the studied properties. The huge amount of possibility offered by the tailoring of the macromolecular structure were exploited for the synthesis of new cholesteric photochromic polymers that can be used as a smart label for the certification of the thermal history of any thermosensitive product. Finally the ATRP synthesis allowed us to synthesize a total new class of material, named molecular brushes: a flat surface covered with an ultra thin layer of polymeric chain covalently bond onto the surface from one end. This new class of materials is of extreme interest as they offer the possibility to tune and manage the interaction of the surface with the environment. In this contest we synthesized both azoaromatic surfaces, growing directly the polymer from the surface, and mixed brushes: surfaces covered with incompatible macromolecules. Both type of surfaces acts as “smart” surfaces: the first it is able to move the orientation of a LC cell by simply photomodulation and, thanks to the robustness of the covalent bond, can be used as a command surface overcoming all the limitation due to the dewetting of the active layer. The second type of surface, functionalized by a grafting-to method, can self assemble the topmost layer responding to changed environmental conditions, exposing different functionality according to different environment.

Preparation and study of magnetic thin film based sub-micron structures

Due to its high Curie temperature of 420K and band structure calculations predicting 100% spin polarisation, Sr2FeMoO6 is a potential candidate for spintronic devices. However, the preparation of good quality thin films has proven to be a non-trivial task. Epitaxial Sr2FeMoO6 thin films were prepared by pulsed laser deposition on different substrates. Differing from previous reports a post-deposition annealing step at low oxygen partial pressure (10-5 mbar) was introduced and enabled the fabrication of reproducible, high quality samples. According to the structural properties of the substrates the crystal structure and morphology of the thin films are modified. The close interrelation between the structural, magnetic and electronic properties of Sr2FeMoO6 was studied. A detailed evaluation of the results allowed to extract valuable information on the microscopic nature of magnetism and charge transport. Smooth films with a mean roughness of about 2 nm have been achieved, which is a pre-requisite for a possible inclusion of this material in future devices. In order to establish device-oriented sub-micron patterning as a standard technique, electron beam lithography and focussed ion beam etching facilities have been put into operation. A detailed characterisation of these systems has been performed. To determine the technological prospects of new spintronics materials, the verification of a high spin polarisation is of vital interest. A popular technique for this task is point contact Andreev reflection (PCAR). Commonly, the charge transport in a transparent metal-superconductor contact of nanometer dimensions is attributed solely to coherent transport. If this condition is not fulfilled, inelastic processes in the constriction have to be considered. PCAR has been applied to Sr2FeMoO6 and the Heusler compound Co2Cr0.6Fe0.4Al. Systematic deviations between measured spectra and the standard models of PCAR have been observed. Therefore existing approaches have been generalised, in order to include the influence of heating. With the extended model the measured data was successfully reproduced but the analysis has revealed grave implications for the determination of spin polarisation, which was found to break down completely in certain cases.

Characterisation of supramolecular structures by novel recoupling methods in solid-state NMR

In this work, solid-state NMR methods suitable for the investigation of supramolecular systems were developed and improved. In this context, special interest was focussed on non-covalent interactions responsible for the formation of supramolecular structures, such as pi-pi interacions and hydrogen-bonds. In the first part of this work, solid-state NMR methods were presented that provide information on molecular structure and motion via the investigation of anisotropic interactions, namely quadrupole and dipole-dipole couplings, under magic-angle spinning conditions. A two-dimensional 2H double quantum experiment was developed, which is performed under off magic-angle conditions and correlates 2H isotropic chemical shifts with quasistatic DQ-filtered line shapes. From the latter, the quadrupole coupling parameters of samples deuterated at multiple sites can be extracted in a site-selective fashion. Furthermore, 7Li quadrupole parameters of lithium intercalated into TiO2 were determined by NMR experiments performed under static and MAS conditions, and could provide information on the crystal geometry. For the determination of 7Li-7Li dipole-dipole couplings, multiple-quantum NMR experiments were performed. The 1H-13C REREDOR experiment was found to be capable of determining strong proton-carbon dipole-dipole couplings with an accuracy of 500~Hz, corresponding to a determination of proton-carbon chemical-bond lengths with picometer accuracy In the second part of this work, solid-state NMR experiments were combined with quantum-chemical calculations in order to aid and optimise the interpretation of experimental results. The investigations on Calix[4]hydroquinone nanotubes have shown that this combined approach can provide information on the presence of disordered and/or mobile species in supramolecular structures. As a second example, C3-symmetric discs arranging in helical columnar stacks were investigated. In these systems, 1H chemical shifts experience large pi-shifts due to packing effects, which were found to be long-ranged. Moreover, quantum-chemical calculations revealed that helicity in these systems is induced by the propeller-like conformation of the core of the molecules.

Solid-state NMR on columnar supramolecular structures

The present work deals with the characterisation of three columnar self-assembled systems, that is, benzene-1,3,5-tricarboxamides, a peripherally thioalkyl-substituted phthalocyanine, and several oligo-(p-phenylenevinylene)s. In order to probe the supramolecular organisation solid-state NMR has been used as the main technique, supported by X-ray measurements, theoretical methods, and thermal analysis. rnrnBenzene-1,3,5-tricarboxamides (BTAs) turned out to be well suited model compounds to study various fundamental supramolecular interactions, such as π-π-interactions, hydrogen bonding, as well as dynamic and steric effects of attached side chains. Six BTAs have been investigated in total, five with a CO-centred amide group bearing different side chains and one with an inverted N-centred amide group. The physical properties of these BTAs have been investigated as a function of temperature. The results indicated that in case of the CO-centred BTAs the stability of the columnar mesophase depends strongly on the nature of the side chains. Further experiments revealed a coplanar orientation of adjacent BTA molecules in the columnar assembly of CO-centred BTAs, whereas the N-centred BTA, showed a deviating not fully coplanar arrangement. These differences were ascribed to distinct hydrogen bonding schemes, involving a parallel alignment of hydrogen bonds in case of CO-centred BTAs and an antiparallel alignment in case of the N-centred counterpart.rnrn The fundamental insights of the supramolecular organisation of BTAs could be partially adapted to an octa-substituted phthalocyanine with thiododecyl moieties. Solid-state NMR in combination with chemical shift calculations determined a tilted herringbone arrangement of phthalocyanine rings in the crystalline phase as well as in the mesophase. Moreover, 1H NMR measurements in the mesophase of this compound suggested an axial rotation of molecules, which is inhibited in the crystalline phase.rnrnAs a third task, the supramolecular assembly of oligo-(p-phenylenevinylene)s of varying length and with different polar head groups have been investigated by a combined X-ray and solid-state NMR study. The results revealed a columnar structure formation of these compounds, being promoted by phase separation of alkyl side chains and aromatic rigid rods. In this system solid-state NMR yielded meaningful insight into the isotropisation process of butoxy and 2-S-methylbutoxy substituted oligo-(p-phenylenevinylene) rods.rn

Comparison of Experimental and Theoretical Structures of a Transition State Analogue Used for the Induction of Anti-Cocaine Catalytic Antibodies

Comparison of the crystal structure of a transition state analogue that was used to raise catalytic antibodies for the benzoyl ester hydrolysis of cocaine with structures calculated by ab initio, semiempirical, and solvation semiempirical methods reveals that modeling of solvation is crucial for replicating the crystal structure geometry. Both SM3 and SM2 calculations, starting from the crystal structure TSA I, converged on structures similar to the crystal structure. The 3-21G(*)/HF, 6-31G*/HF, PM3, and AM1 calculations converged on structures similar to each other, but these gas-phase structures were significantly extended relative to the condensed phase structures. Two transition states for the hydrolysis of the benzoyl ester of cocaine were located with the SM3 method. The gas phase calculations failed to locate reasonable transition state structures for this reaction. These results imply that accurate modeling of the potential energy surfaces for the hydrolysis of cocaine requires solvation methods.