Sínteses e caracterizações de materiais microporosos com estrutura cristalográfica mista e suas aplicações como catalisadores em reações de conversão de biomassa em produtos de química fina

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Structural refinement, optical and microwave dielectric properties of BaZrO3

In this work, barium zirconate (BaZrO3) ceramics synthesized by solid state reaction method and sintered at 1670 degrees C for 4 h were characterized by X-ray diffraction (XRD), Rietveld refinement, and Fourier transform infrared (FT-IR) spectroscopy. XRD patterns, Rietveld refinement data and FT-IR spectra which confirmed that BaZrO3 ceramics have a perovskite-type cubic structure. Optical properties were investigated by ultraviolet-visible (UV-vis) absorption and photoluminescence (PL) measurements. UV-vis absorption spectra suggested an indirect allowed transition with the existence of intermediary energy levels within the band gap. Intense visible green PL emission was observed in BaZrO3 ceramics upon excitation with a 350 nm wavelength. This behavior is due to a majority of deep defects within the band gap caused by symmetry breaking in octahedral [ZrO6] clusters in the lattice. The microwave dielectric constant and quality factor were measured using the method proposed by Hakki-Coleman. The dielectric resonator antenna (DRA) was investigated experimentally and numerically using a monopole antenna through an infinite ground plane and Ansoft's high frequency structure simulator software, respectively. The required resonance frequency and bandwidth of DRA were investigated by adjusting the dimension of the same material. (C) 2011 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Latent track radius of PTFE irradiated with high energy ion beam

PTFE foils were irradiated with different ion beams (Xe, Au and U) with energies up to 1.5 GeV and fluences between 1 x 10(8) and 1 x 10(13) ions/cm(2) at room temperature. The induced modifications in the polymer were analyzed by FTIR, UV-Vis spectroscopy, and XRD. In the FTIR spectra, the CF2 degradation accompanied by the formation of CF3 terminal and side groups were observed. In the UV-Vis spectra, the observed increase in the absorption at UV wavelengths is an indication of polymer carbonization. From XRD, the amorphization of the material was evidenced by the decrease in the intensity of the main diffraction peak. An exponential fit of the intensity of the IR absorption peaks resulted in the following values: 2.9 +/- 0.8; 4.5 +/- 0.9 and 5.6 +/- 0.8 nm for the latent track radius after irradiation with Xe, Au and U beams, respectively. (C) 2011 Elsevier B.V. All rights reserved.

Raman spectroscopy and DFT calculations of para-coumaric acid and its deprotonated species

An electronic and vibrational spectroscopic analysis of p-coumaric acid (HCou) and its deprotonated species was performed by UV-vis and Raman, respectively, and the results were supported by density functional theory (OFT) calculations. Electronic UV-vis spectral data of HCou solutions show that the deprotonation of the carboxyl group (Cou(-)) leads to a blue shift of the lowest energy electronic transition in comparison to the neutral species, whereas the subsequent deprotonation of the phenolic moiety (Cou(2-)) carries out to a more delocalized chromophore. The DFT geometric parameters calculations suggest that the variation in the electronic delocalization for the three organic species is due to different contribution of a quinoid structure that is significantly distorted in the case of Cou(2-). The Raman data of HCou and its sodium salts show that the main spectral features that allow to differentiate the three organic species are those involving the styrene nu(C=C)(sty) vibration at 1600cm(-1) region. Even though the Raman spectra of the sodium salts of Cou(-) and Cou(2-) anions show subtle differences, the appearing of a band at ca. 1598cm(-1) in the Na(2)Cou spectrum, assigned to a mode involving the carboxylate asymmetric stretching, nu(as)(COO), and the styrene stretching, nu(C=C)(sty), is quite characteristic, as confirmed by the theoretical Raman spectrum. Considering that p-coumaric acid is an archetypical phenolic compound with several biological activities that essentially depend upon the medium pH, Raman spectroscopy results reported in this work can provide a proper way to characterize such important phytochemical compound in different protonation states. In order to complement the characterization of the sodium salts, X-ray diffraction (XRD) and thermal analysis were performed. (C) 2011 Elsevier B.V. All rights reserved.

Cluster Coordination and Photoluminescence Properties of alpha-Ag2WO4 Microcrystals

In this paper, we report our initial research to obtain hexagonal rod-like elongated silver tungstate (alpha-Ag2WO4) microcrystals by different methods [sonochemistry (SC), coprecipitation (CP), and conventional hydrothermal (CH)] and to study their cluster coordination and optical properties. These microcrystals were structurally characterized by X-ray diffraction (XRD), Rietveld refinements, Fourier transform infrared (FT-IR), X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopies. The shape and average size of these alpha-Ag2WO4 microcrystals were observed by field-emission scanning electron microscopy (FE-SEM). The optical properties of these microcrystals were investigated by ultraviolet-visible (UV-vis) spectroscopy and photoluminescence (PL) measurements. XRD patterns and Rietveld refinement data confirmed that alpha-Ag2WO4 microcrystals have an orthorhombic structure. FT-IR spectra exhibited four IR-active modes in a range from 250 to 1000 cm(-1). XANES spectra at the W L-3-edge showed distorted octahedral [WO6] clusters in the lattice, while EXAFS analyses confirmed that W atoms are coordinated by six O atoms. FE-SEM images suggest that the alpha-Ag2WO4 microcrystals grow by aggregation and the Ostwald ripening process. PL properties of alpha-Ag2WO4 microcrystals decrease with an increase in the optical band-gap values (3.19-3.23 eV). Finally, we observed that large hexagonal rod-like alpha-Ag2WO4 microcrystals prepared by the SC method exhibited a major PL emission intensity relative to alpha-Ag2WO4 microcrystals prepared by the CP and CH methods.

Adsorption of caffeic acid on titanium dioxide: A spectroscopic study

Caffeic acid is an ortho-phenol found in vegetable tissues presenting important properties such as carcinogenesis inhibitor, anti-oxidant, anti-viral, anti-inflammatory and anti-rheumatic actions. It was observed that caffeic acid was not degraded in daylight during the adsorption on TiO2 at pH 4.8. The adsorption fit very well to a Brunauer-Emmett-Teller isotherm equation with a monolayer coverage of 68.15 mg(CA) g(TiO2)(-1) and saturation coverage of 195.4 mg(CA) g(TiO2)(-1). A strong adsorption of caffeic acid was verified on TiO2 for the dry solid obtained from the mixture. The Raman and IR spectroscopies revealed that the adsorption should occur through the interaction of the diphenol oxygens with contribution of CC double bond of the acrylic group, however, the carboxylic acid group did not have participation in the adsorption. (C) 2012 Elsevier B.V. All rights reserved.

Synthesis and characterization of polymers containing oligothiophenes

In the present work a series of thiophene oligomers of three and six thiophene units were synthesized, starting from thiophene, and characterized. Polymers containing these electroative side groups were then prepared by two strategies. The oligomers were attached to existing polymer systems and were connected to a polymerizable unit leading to monomer containing the oligothiophenes as side groups. Subsequently the properties of the monomers and the polymers were investigated. A butylcellulose derivative carrying terthienyl side chains (BCTTE, 26) was synthesized starting from cellulose acetate and 5-(2-chloroethyl)-2,2':5',2'-terthiophene (4). The polymer had a degree of substitution (DS) of the butyl and terthienyl side chains of DSbutyl = 1.9 and DSterth = 0.35, respectively. It was successfully spread on a Langmuir-Blodgett (LB) trough and then transferred to several solid substrates. X-rays reflectometry showed an ordered architecture of the cellulose backbones. However, the terthiophene side groups were found as isotropically aligned by polarized UV-Vis spectroscopy. When used as anode material in the electropolymerization of 3-pentylthiophene (28), polythiophene was grafted onto the cellulose backbone through the terthienyl side groups. The polythiophene chains showed an average anisotropic alignment of 20 % along the LB dipping direction, calculated by means of polarized UV-Vis spectroscopy. A second butylcellulose derivative carrying sexithienyl side chains (BCST) was synthesized and investigated, starting from butylcellulose and 2-[b ', b ''-dipentyl-5'''-(2-hydroxyethyl)-2,2': 5',2':5',2'':5'',2'':5'',2'''-sexithiophen-5-yl]-ethyl p-toluensulfonate (7). The polymer showed formation of stable LB monolayers at the air-water interface, but its transfer onto solid substrates was not successful. A poly(p-phenylene-ethynylene) bearing sexithienyl side chains (BzAcST, 31) was prepared by reaction of the two monomers 2-[b ', b ''-dipentyl-5'''-(2-hydroxyethyl)-2,2': 5',2':5',2'':5'',2'':5'',2'''-sexithiophen-5-yl]-ethyl 2,5-diiodobenzoate (15) and 2-[b', b ''-dipentyl-5'''-(2-hydroxyethyl)-2,2':5',2':5',2'':5'',2'':5'',2'''-sexithiophen-5-yl]-ethyl 2,5-diethynylbenzoate (18). The polymer was obtained as insoluble product. Upon oxidation with FeCl3 (doping) of the polymer suspension, BzAcST showed an electrical conductivity of ó = 2.5 . 10 -6 S/cm, a typical value for semiconductors. The IR spectrum of the doped polymer presented the diagnostic bands of oxidized sexithiophene in good agreement with literature results. Along with the monomer and polymer synthesis, an a,a '-disubstituted sexithiophene, b ', b ''-dipentyl-5,5'''-bis-(2-hydroxyethyl)-2,2':5',2':5',2'':5'',2'':5'',2'''-sexithiophene (6a),was synthesized and characterized. The UV-Vis absorption of the chromophore wasinvestigated as a function of temperature and different solvents, showing a blue-shift of the absorption maximum with increasing temperature and a red-shift changing the solvent from hexane to ethanol to toluene. Monitoring the change of the UV-Vis spectrum upon electrochemical oxidation, the oxidized chromophore showed a new broad absorption band, red shifted with respect to the p -p* transition of the neutral state. Upon reduction, the new band disappeared and the UV-Vis spectrum of the chromophore was restored. Such oxidation-reduction cycles were totally reversible. This feature, together with the absorption maximum falling in the visible region, makes this chromophore a suitable compound for the development of an electrochemical sensor.Attempts to polymerize acrylic monomers carrying sexythienyl side chains both via radical polymerization, as in the case of 2-[b ', b ''-dipentyl-5'''-(2-hydroxyethyl)-2,2': 5',2':5',2'':5'',2'':5'',2'''-sexithiophen-5-yl]-ethyl acrylate (8), and anionic polymerization, as in the case of 2-{b ', b ''-dipentyl-5'''-[2-(tertbutyldimethylsiloxy)ethyl]-2,2':5',2':5',2'':5'',2'': 5'',2''' -sexithiophen-5-yl}-ethylacrylate (29), were not successful, probably due to the steric hindrance of the oligothiophene side group. However, due to the time consuming and therefore restricted availability of the monomers, a screening of the polymerization conditions towards the formation of polymeric material was not possible.

Synthese und Charakterisierung photoschaltbarer Gelbildner

Zusammenfassung Um photoschaltbare Gelbildner zu synthetisieren wurde auf bereits bekannte Gelbildner zurückgegriffen und eine Azobenzolgruppe, als photoschaltbare Einheit eingebaut. Die Modifizierung der Alkylsemicarbazide führte zu 7 Azosemicarbaziden (36-42), die alle gelbildende Eigenschaften haben. Die Gele des Alkylsemicarbazids 1 und der Azosemicarbazide 37 und 38 erwiesen sich als die stabilsten, weshalb an ihnen die meisten Untersuchungen durchgeführt wurden. Ihre Struktur ist in Abbildung 1 noch einmal aufgeführt. Die Alkylsemicarbazide vergelen Toluol, 1,2-Dichlorbenzol, Decalin, Tetralin und Cyclohexan. Die minimalen Gelbildnerkonzentration geht dabei von ~0,5 Gew.% für Toluol bis ~10 Gew.% für Tetralin und Cyclohexan. Die Azosemicarbazide 36-40 vergelen Toluol und Tetralin mit ~10 Gew.%, 1,2-Dichlorbenzol und Decalin mit ~4-7 Gew.Durch den Vergleich verschiedener Kristallstrukturen (von 1, 5, 19 und 43) und einer Röntgenkleinwinkelmessung eines Gels wurden zwei mögliche Kristallstrukturen für 37 vorgestellt. Die Tatsache, dass die IR-Spektren aller Semicarbazide im Bulk und als Gel sehr ähnliche Absorptionsbanden im Bereich der N-H-Schwingungen besitzen, zeigt, dass das vorgestellt Wasserstoffbrückenmotiv (Kapitel 4.1, Schema 4.1) für alle Semicarbazide nahezu gleich ist. Des Weiteren konnte ein Zusammenhang von der minimalen Gelbildner-konzentration, dem Schmelzpunkt und der Struktur des Gelnetz-werks gefunden werden. Je feiner das Netzwerk und damit je größer die Oberfläche, desto niedriger die minimale Gelbildnerkonzentration und desto niedriger der Schmelzpunkt der Gele. Gele mit Decalin fallen dabei durch eine andere Morphologie und besonders hohe Schmelzpunkte auf (Abbildung 2). Die Photoschaltbarkeit wurde im Gel mit organischen Lösungsmitteln und mit den Flüssigkristallmischungen durch UV/Vis-Messungen, Polarisationsmikroskopie, sowie durch die Bestimmung der Schaltzeiten und der Schwellspannung für LC II-Gele nachgewiesen. Erste dielektrische Messungen an einem LC II-Gel zeigen, dass die Goldstone-Mode im Gel unterdrück wird. Diese Ergebnisse sollen mit weiteren Untersuchungen untermauert werden.

Electrostatically self-assembled nanoparticles based on biomolecules

In this work, two different systems were investigated to develop fundamental understanding of the self-assembly behavior of polyelectrolytes and small organic counterions with a certain geometry. Complexes formed were characterized by light scattering in solution, as well as UV-Vis spectroscopy, analytical ultracentrifugation, gel electrophoresis, zeta potential and IR spectroscopy. The morphologies of the aggregates were observed by AFM in dried state on surface. The charge ratio, the valence and the structure of the counterion were shown to represent key parameters in the complexation. The influence of polyelectrolyte type and molecular weights was also determined for the structure formed.rnrnOne system was mainly focused on the association of double-strand DNA with non-intercalating divalent and tetravalent organic counterions. The other model system involved linear NaPSS and oligolysines. In addition, various influences on the morphology of the charged self-assembly complexes in AFM studies were discussed. It was shown that electrostatic self-assembly of DNA and non-intercalating counterions as well as of a linear synthetic polyelectrolyte with oligolysine counterions that can build mutual hydrogen bonds can yield supramolecular aggregates of a defined size. Various morphologies (flower-like, rod-like, toroidal and spherical) of the assemblies were obtained for different combinations of polyelectrolyte and counterions. Results presented in this work are of importance for the fundamental understanding of the association behavior of various polyelectrolytes and organic counterions. The selection of biopolymers for the study may give an opportunity to transfer the basic research results into biological applications, such as gene therapy or drug delivery.rn

Die Vielseitigkeit von Carbazol in pi-konjugierten Materialien: Makrozyklen, Doppelstrang-Strukturen und Donor-Akzeptor-Copolymere

In dieser Arbeit wurden die vielfältigen Anwendungsmöglichkeiten von Carbazol-reichen Verbindungen in unterschiedlichen Architekturen von pi-konjugierten Materialien untersucht. Die Darstellung der Makrozyklen in Kapitel 1 erfolgte über eine templatunterstützte Synthese, da die ausschließlich über ihre para-Position verknüpften Einheiten einen Zugang über ihre Geometrie nicht erlaubten. Cyclododeca-2,7-fluoren wurde als zyklische Modellverbindung für die zahlreichen bekannten linearen Oligo- und Polyfluorene dargestellt, um den Einfluss der Ringstruktur auf die optischen Eigenschaften dieser blau emittierenden Verbindungen zu untersuchen. Motiviert von den geringen Ausbeuten bei der Zyklisierung des Rings unter Yamamoto-Bedingungen wurde nach einer alternativen Kupplungsreaktion gesucht, die den Zugang zu größeren Substanzmengen erlaubt. Die Einführung von terminalen Ethinylgruppen an die zu verknüpfenden Bausteine erlaubte über die Glaser-Eglinton-Reaktion nicht nur eine Verbesserung der Reaktionsausbeute um den Faktor 10, sondern gleichzeitig auch die Erweiterung des Durchmessers auf rund 5 nm. Demonstriert wurde dies anhand der Darstellung von Cyclo[tetrakis(2,7-diethinyltriscarbazol)] und Cyclo[tetrakis(2,7-diethinyltrisfluoren)].rnDer zweite Abschnitt der Dissertation befasste sich mit ausgedehnten zweidimensionalen Strukturen, zu denen auch mehrsträngige Polymere zählen. Für die Darstellung eines Doppelstrang-Polymers mit hoher Periodizität in den beiden in regelmäßigen Abständen verknüpften Strängen wurde ein neues Konzept entwickelt, dass den Zugang zu solchen Verbindungen erlauben sollte. Dieses basierte auf einem vierfach funktionalisierten Carbazol-Makromonomer. Die Polymerisationen wurden in zwei Schritten über Glaser-Eglinton-Reaktionen durchgeführt. Um unkontrollierte Kupplungen zu vermeiden, wurden zwei der vier reaktiven Positionen am Monomer zunächst über Schutzgruppen maskiert und nach der ersten Polymerisation wieder aktiviert. Neben diesem Ansatz über oxidative Ethinylkupplungen wurde auch eine Organometall-Variante mit einem Platin-Komplex im Polymerrückgrat vorgestellt. rnIm dritten Kapitel wurde die Darstellung von Donor-Akzeptor-Polymeren mit niedriger Bandlücke für den Einsatz in organischen Solarzellen besprochen. Im Gegensatz zu den bisherigen Ansätzen in der Literatur wurden hier ganz gezielt Donor- und Akzeptor-Einheiten mit einer Länge von mindestens 1,5 nm synthetisiert und kombiniert, um zu untersuchen, welche Auswirkungen der Einsatz solcher Makromonomere auf die Eigenschaften der Materialien hat. Dabei bestand der Akzeptor-Baustein in drei Polymeren aus Bis[2,7-di-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9,18,18-tetraoctylindeno[1,2-b]-yl]-indeno[1,2-b]fluoren-12,15-dion, während die Donor-Stärke durch den Übergang von einem reinen leiterverbrückten Carbazol-Monomer über eine gemischte Carbazol-Thiophen-Einheit hin zu einem reinen Thiophen-Precursor variiert wurde. Dabei zeigte das Polymer mit Thiophen als Donor den höchsten Zellwirkungsgrad von 0,41 %.rn

Polimeri tiofenici funzionali e loro applicazioni nel fotovoltaico

Recentemente, sempre più attenzione è stata rivolta all' utilizzo di coloranti organici come assorbitori di luce per la preparazione di strati fotoattivi in celle solari organiche (OPV). I coloranti organici presentano un'elevata abilità nella cattura della luce solare grazie all'elevato coefficiente di estinzione molare e buone proprietà fotofisiche. Per questi motivi sono eccellenti candidati per l'incremento della conversione fotoelettrica in OPV. In questa tesi viene descritta una nuova strategia per l'incorporazione di derivati porfirinici in catena laterale a copolimeri tiofenici. Gli studi svolti hanno dimostrato che poli(3-bromoesil)tiofene può essere variamente funzionalizzato con idrossitetrafenilporfirina (TPPOH), per l'ottenimento di copolimeri utilizzabili come materiali p-donatori nella realizzazione di OPV. I copolimeri poli[3-(6-bromoesil)tiofene-co-(3-[5-(4-fenossi)-10,15,20-trifenilporfirinil]esil tiofene] P[T6Br-co-T6TPP] contenenti differenti quantità di porfirina, sono stati sintetizzati sia con metodi non regiospecifici che regiospecifici, con lo scopo di confrontarene le proprietà e di verificare se la strutture macromolecolare che presenta una regiochimica di sostituzione sempre uguale, promuove o meno il trasporto della carica elettrica, migliorando di conseguenza l'efficienza. E' stato inoltre effettuato un ulteriore confronto tra questi derivati e derivati simili P[T6H-co-T6TPP] che non contengono l'atomo di bromo in catena laterale con lo scopo di verificare se l'assenza del gruppo reattivo, migliora o meno la stabilità termica e chimica dei film polimerici, agendo favorevolmete sulle performance dei dispositivi fotovoltaici. Tutti i copolimeri sono stati caratterizzati con differenti tecniche: spettroscopia NMR, FT-IR e UV-Vis, analisi termiche DSC e TGA, e GPC. Le celle solari Bulk Heterojunction, preparate utilizzando PCBM come materiale elettron-accettore e i copolimeri come materilai elettron-donatori, sono state testate utilizzando un multimetro Keithley e il Solar Simulator.

Silk Fibroin: a biopolymer platform for innovative pharmaceutical formulation and biomedical devices.

The protein silk fibroin (SF) from the silkworm Bombyx mori is a FDA-approved biomaterial used over centuries as sutures wire. Importantly, several evidences highlighted the potential of silk biomaterials obtained by using so-called regenerated silk fibroin (RSF) in biomedicine, tissue engineering and drug delivery. Indeed, by a water-based protocol, it is possible to obtain protein water-solution, by extraction and purification of fibroin from silk fibres. Notably, RSF can be processed in a variety of biomaterials forms used in biomedical and technological fields, displaying remarkable properties such as biocompatibility, controllable biodegradability, optical transparency, mechanical robustness. Moreover, RSF biomaterials can be doped and/or chemical functionalized with drugs, optically active molecules, growth factors and/or chemicals In this view, activities of my PhD research program were focused to standardize the process of extraction and purification of protein to get the best physical and chemical characteristics. The analysis of the chemo-physical properties of the fibroin involved both the RSF water-solution and the protein processed in film. Chemo-physical properties have been studied through: vibrational (FT-IR and Raman-FT) and optical (absorption and emission UV-VIS) spectroscopy, nuclear magnetic resonance (1H and 13C NMR), thermal analysis and thermo-gravimetric scan (DSC and TGA). In the last year of my PhD, activities were focused to study and define innovative methods of functionalization of the silk fibroin solution and films. Indeed, research program was the application of different methods of manufacturing approaches of the films of fibroin without the use of harsh treatments and organic solvents. New approaches to doping and chemical functionalization of the silk fibroin were studied. Two different methods have been identified: 1) biodoping that consists in the doping of fibroin with optically active molecules through the addition of fluorescent molecules in the standard diet used for the breeding of silkworms; 2) chemical functionalization via silylation.

Pi-konjugierte Plasmapolymere als organische Halbleiter durch vorstrukturierte single-source-Precursoren

Die vorliegende Arbeit behandelt die Entwicklung einer neuartigen Synthesestrategie von π-konjugierten Plasmapolymeren durch die Anwendung von vorstrukturierten aromatischen Precursoren und gepulsten Niederdruckplasmen. Es gelang erstmals die strukturtreue Synthese von π-konjugierten organischen Plasmapolymeren mit dem vollkommenen Erhalt der aromatischen Funktionalität und der selektiven para-Verknüpfung aromatischer Einheiten durch geeignete Heteroatome. Hierbei kamen 1,4-Dithiophenol zur Synthese von Plasmapoly(p-phenylensulfid) und 4-Iodanilin zur Synthese von Plasmapolyanilin zur Anwendung. Die mit hoher Präzision abgeschiedenen Filme konnten sowohl postsynthetisch als auch in situ p-dotiert werden. Die chemischen Strukturen sowie deren physikalisch-chemischen Eigenschaften konnten vor allem mittels Röntgenphotoelektronen-, UV-VIS-NIR-, IR-, NMR-, ESR- und Impedanz-Spektroskopie aufgeklärt werden. Die synthetisierten dotierten Plasmapolymere zeigten eindeutig ohmsche Leistungsmechanismen, teilweise mit einer Leitfähigkeitserhöhung von bis zu 8 Dekaden gegenüber dem undotierten konventionellen Polymer.

Synthesis of bis(3-{[2-(allyloxy)ethoxy]methyl}-2,4,6-trimethylbenzoyl)(phenyl)phosphine oxide - a tailor-made photoinitiator for dental adhesives

Because of the poor solubility of the commercially available bisacylphosphine oxides in dental acidic aqueous primer formulations, bis(3-{[2-(allyloxy)ethoxy]methyl}-2,4,6-trimethylbenzoyl)(phenyl)phosphine oxide (WBAPO) was synthesized starting from 3-(chloromethyl)-2,4,6-trimethylbenzoic acid by the dichlorophosphine route. The substituent was introduced by etherification with 2-(allyloxy)ethanol. In the second step, 3-{[2-(allyloxy)ethoxy]methyl}-2,4,6-trimethylbenzoic acid was chlorinated. The formed acid chloride showed an unexpected low thermal stability. Its thermal rearrangement at 180 ° C resulted in a fast formation of 3-(chloromethyl)-2,4,6-trimethylbenzoic acid 2-(allyloxy)ethyl ester. In the third step, the acid chloride was reacted with phenylphosphine dilithium with the formation of bis(3-{[2-(allyloxy)ethoxy]methyl}-2,4,6-trimethylbenzoyl)(phenyl)phosphine, which was oxidized to WBAPO. The structure of WBAPO was confirmed by ¹H NMR, ¹³C NMR, ³¹P NMR, and IR spectroscopy, as well as elemental analysis. WBAPO, a yellow liquid, possesses improved solubility in polar solvents and shows UV-vis absorption, and a high photoreactivity comparable with the commercially available bisacylphosphine oxides. A sufficient storage stability was found in dental acidic aqueous primer formulations.

Syntheses and structures of molybdenum and tungsten complexes capable of epoxidaton and copper coordination polymers and dendrimers

We are interested in the syntheses of new complexes and in their characterization by single crystal X-ray diffraction techniques. Once we understand the structures, studies aimed at understanding uses of these complexes in the field of catalytic epoxidation using complexes soluble in water and syntheses of thin films (not assessed) were conducted. The syntheses, characterization and catalytic properties of a series of mononuclear, dinuclear and tetranuclear molybdenum and tungsten oxo complexes are described. The syntheses and structural characterization of two copper coordination polymers with 3,5-dihydroxylbenzoate ligand, and five paddlewheel shaped copper dendrimers coordinated with Fréchet-type dendrons are also detailed. The background of this dissertation is outlined in Chapter 1. Chapter 2 describes the syntheses, and characterization of two new mononuclear molybdenum(VI) and tungsten(VI) oxo complexes, MoO2Cl2(OPPh2CH2OH)2, and WO2Cl2(OPPh2CH2OH)2, bearing hydrophilic phosphine oxide ligand. The catalytic properties of these complexes for the epoxidation of cis-cyclooctene were also studied. Two new dinuclear molybdenum(VI) and tungsten(VI) oxo complexes Mo2O4Cl2[(HOCH2)PhPOO]2, and (CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2, bearing organophosphinate ligand are described in Chapter 3 and 4. Chapter 4 and 5 describes the syntheses and characterization of tetranuclear molybdenum(V) oxo complexes bearing various organophosphinate ligands. The catalytic abilities of these complexes for the epoxidation of cis-cyclooctene in the presence of hydrogen peroxide as oxidant were explored as well. Various spectroscopic methods, such as IR, UV-vis, and NMR are used to characterize the nature of these complexes. Crystal structures of compounds MoO2Cl2(OPPh2CH2OH)2, WO2Cl2(OPPh2CH2OH)2, Mo2O4Cl2[(HOCH2)PhPOO]2, (CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2, and Mo4(µ3-O)4(µ-O2PR2)4O4 (R=Ph, Me, ClCH2, o-C6H4(CH2)2) are also presented. The syntheses, and structural characterization of three copper(II) coordination polymers bearing 3,5-dihydroxybenzoate ligand are described in Chapter 6. Two copper(II) coordination polymers, [Cu2(3,5-dhb)2(pyridine)4]n, and [Cu2(3,5-dhb)4]n were afforded based on different amount of pyridine used in the reaction. The structures of these complexes are further built into 2D or 3D networks via inter or intra hydrogen bonds. The syntheses and structural characterization of the zinc(II) monomer, Zn(3,5-dhb)2(pyridine)2 is also described in this Chapter. Chapter 7 describes the syntheses, and characterization of five dendronized dicopper complexes bearing different generations of Fréchet-type dendrons. The structures of 3,5- bis(benzoyloxl)benzoic acid, 3,5-(PhCOO)2PhCOOH (G1), Cu2(3,5-dhb)4(THF)2, Cu2(G1)4(pyridine)2, and Cu2(G1)4(CH3OH)2 were characterized unambiguously by single X-ray diffraction. In addition, all compounds were characterized by FT-IR, UV-vis spectroscopy and elemental analyses.