Synthesis and surface characterization of metal (Mn, Ti) hexacyanoferrate electrodes

Due to the limited resources of lithium, new chemistries based on the abundant and cheap sodium and even zinc have been proposed for the battery market. Prussian Blue Analogues (PBAs) are a class of compounds which have been explored for many different applications because of their intriguing electrochemical and magnetic properties. Manganese and titanium hexacyanoferrate (MnHCF and TiHCF) belong to the class of PBAs. In this work, MnHCF and TiHCF electrodes were synthetized, cycled with cyclic voltammetry (CV) in different setups and subsequently, the surfaces were characterized with X-ray Photoelectron Spectroscopy (XPS). The setups chosen for CVs were coin cell with zinc aqueous solution for the MnHCF series, three-electrode cell and symmetric coin cell with sodium aqueous solution for the TiHCF series. The electrodes were treated with different number of cycles to evaluate the chemical changes and alterations in oxidation states during cycling.

Synthesis, characterization and potential applications of novel metal-organic frameworks

​The research work described in this thesis concerns the synthesis, characterization, and applications of two kinds of metal-organic frameworks (MOFs), Copper based MOF (Cu-MOF) and zirconium based MOF (Zr-MOF) functionalized with new linkers. ​The common thread of this research project can be summarized in three work phases: ​first, the synthesis and characterization of new organic linkers is described, followed by the presentation of the different optimization conditions for the MOFs synthesis. ​Second, the new materials were fully characterized using several complementary techniques, such as infrared (ATR-FTIR) and Raman spectroscopy, X-ray powder diffraction spectroscopy (PXRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), atomic absorption spectroscopy (AAS) as well as thermal and surface area measurements. ​Final, to obtain a complete work the possible environmental applications of the new materials were explored.

A New Platinum Complex With Tryptophan: Synthesis, Structural Characterization, Dft Studies And Biological Assays In Vitro Over Human Tumorigenic Cells.

A new platinum(II) complex with the amino acid L-tryptophan (trp), named Pt-trp, was synthesized and characterized. Elemental, thermogravimetric and ESI-QTOF mass spectrometric analyses led to the composition [Pt(C11H11N2O2)2]⋅6H2O. Infrared spectroscopic data indicate the coordination of trp to Pt(II) through the oxygen of the carboxylate group and also through the nitrogen atom of the amino group. The (13)C CP/MAS NMR spectroscopic data confirm coordination through the oxygen atom of the carboxylate group, while the (15)N CP/MAS NMR data confirm coordination of the nitrogen of the NH2 group to the metal. Density functional theory (DFT) studies were applied to evaluate the cis and trans coordination modes of trp to platinum(II). The trans isomer was shown to be energetically more stable than the cis one. The Pt-trp complex was evaluated as a cytotoxic agent against SK-Mel 103 (human melanoma) and Panc-1 (human pancreatic carcinoma) cell lines. The complex was shown to be cytotoxic over the considered cells.

Preparation and characterization of Mo/W bimetallic carbides by using different synthesis methods

Molybdenum and tungsten bimetallic oxides were synthetized according to the following methods: Pechini, coprecipitation and solid state reaction (SSR). After the characterization, those solids were carbureted at programmed temperature. The carburation process was monitored by checking the consumption of carburant hydrocarbon and CO produced. The monitoring process permits to avoid or to diminish the formation of pirolytic carbon.

Synthesis, characterization, and bactericidal properties of composites based on crosslinked resins containing silver

Two different commercial crosslinked resins (Amberlite GT73 and Amberlite IRC748) were employed for anchoring silver. The -SH and -N(CH2COOH)2 groups, respectively, present on these resins were used for Ag+ chelation from an aqueous solution. The Ag+ ions were reduced with three different reductants: hydrazine, hydroxylamine, and formaldehyde (under an alkaline pH). The produced composites were characterized with thermogravimetry/differential thermogravimetry and scanning electron microscopy combined with a backscattered scanning electron detector. Energy-dispersive X-ray spectroscopy coupled to scanning electron microscopy allowed the observation of submicrometer particles of silver, and chemical microanalysis of emitted X-rays revealed the presence of metal on the internal and external surfaces of the composite microspheres. The amount of incorporated silver was determined by titration. The antibacterial activity of the silver/resin composites was determined toward 10(3)-10(7) cells/mL dilutions of the auxotrophic AB1157 Escherichia coli strain; the networks containing anchored submicrometer silver particles were completely bactericidal within a few minutes because of the combined action of silver and functional groups of the resins. (c) 2007 Wiley Periodicals, Inc.

Metal-directed synthesis routes to a 16-membered tetraazamacrocycle with two pendant primary amine groups

The reaction of the bis(propane-1,3-diamine)copper(II) ion with paraformaldehyde and nitroethane in dry methanol under basic conditions produces a macrocyclic product, (cis-3,11-dimethyl-3,11-dinitro-1,5,9,13-tetraazacyclohexadecane)copper(II) perchlorate, in low yield, compared with the good yield obtained in the parallel chemistry possible even under aqueous conditions using palladium(II) as a template. The palladium complex was reduced with zinc amalgam in dilute aqueous acid to yield the metal-free 16-membered macrocyclic hexaamine, in this case re-complexed and characterised by an X-ray crystal structure as the (cis-3,11-dimethyl-1,5,9,13-tetraazacyclohexadecane-3,11-diamine)copper(II) perchlorate. The copper ion is found in a tetragonally elongated and trigonally-distorted octahedral environment, with all six of the ligand nitrogens coordinated, the two primary amine pendant groups occupying cis sites. (C) 2000 Elsevier Science S.A. All rights reserved.

Synthesis and characterization of trans-[Ru(NO)Cl(L)(4)](PF(6))(2) (L = isonicotinamide; 4-acetylpyridine) and related species

The trans-[RUCl(2)(L)(4)], trans-[Ru(NO)Cl (L)(4)](PF(6))(2) (L = isonicotinamide and 4-acetylpyridine) and trans-[Ru(NO)(OH)(py)(4)]Cl(2) (py = pyridine) complexes have been prepared and characterized by elemental analysis, UV-visible, infrared, and (1)H NMR spectroscopies, and cyclic voltammetry. The MLCT band energies of trans-[RUCl(2)(L)(4) increase in the order 4-acpy < isn < py. The reduction potentials of trans-[RuCl(2)(L)(4)] and trans-[Ru(NO)Cl(L)(4)](2+) increase in the order py < isn < 4-acpy. The stretching band frequency. v(NO), of the nitrosyl complexes ranges from 1913 to 1852 cm(-1) indicating a nitrosonium character for the NO ligand. Due to the large pi-acceptor ability of the equatorial ligands, the coordinated water is much more acidic in the water soluble trans-[Ru(NO)(H(2)O)(py)(4)](3+) than in trans-[Ru(NO)(H(2)O)(NH(3))(4)](3+) (C) 2009 Elsevier B.V. All rights reserved.

Synthesis and structural properties of patellamide a derivatives and their copper(II) compounds

The synthesis, characterization and copper(II) coordination chemistry of three new cyclic peptide ligands, PatJ(1) (cyclo-(Ile -Thr- (Gly)Thz-lle-Thr(Gly)Thz)), PatJ(2) (cyclo-(Ile-Thr(Gly)Thz-(D)-Ile-Thr-(Gly)Thz)), and PatL (cyclo-(Ile-Ser-(Gly)Thz-Ile-Ser(Gly)Thz)) are reported. All of these cyclic peptides and PatN (cyclo-(Ile-Ser(Gly)Thz-Ile-Thr-(Gly)Thz)) are derivatives of patellamide A and have a [24]azacrown-8 macrocyclic structure. All four synthetic cyclic peptides have two thiazole rings but, in contrast to patellamide A, no oxazoline rings. The molecular structure of PatJ1, determined by X-ray crystallography, has a saddle conformation with two close-to-co-parallel thiazole rings, very similar to the geometry of patellamide D. The two coordination sites of PatJ1 with thiazole-N and amide-N donors are each well preorganized for transition metal ion binding. The coordination of copper(II) was monitored by UV/Vis spectroscopy, and this reveals various (meta)stable mono- and dinuclear copper(II) complexes whose stoichiometry was confirmed by mass spectra. Two types of dinuclear copper(II) complexes, [Cu-2(H4L)(OH2)(n)](2+) (n = 6, 8) and [Cu-2(H4L)(OH2)(n)] (n=4, 6; L=PatN, PatL, PatJ1, PatJ2) have been identified and analyzed structurally by EPR spectroscopy and a combination of spectra simulations and molecular mechanics calculations (MM-EPR). The four structures are similar to each other and have a saddle conformation, that is, derived from the crystal structure of PatJ(1) by a twist of the two thiozole rings. The small but significant structural differences are characterized by the EPR simulations.

Synthesis, structural characterization and leishmanicidal activity evaluation of ferrocenyl N-heterocyclic compounds

Agência Financiadora: FCT - PTDC/QUI/72656/2006 ; SFRH/BPD/27454/2006; SFRH/BPD/44082/2008; SFRH/BPD/41138/2007

Benzo[c]thiophene chromophores linked to cationic Fe and Ru derivatives for NLO materials: synthesis characterization and quadratic hyperpolarizabilities

5-Monocyclopentadienyliron(II)/ruthenium(II) complexes of the general formula [M(5-C5H5)(PP)(L1)][PF6] {M = Fe, PP = dppe; M = Ru, PP = dppe or 2PPh3; L1 = 5-[3-(thiophen-2-yl)benzo[c]thiophenyl]thiophene-2-carbonitrile} have been synthesized and studied to evaluate their molecular quadratic hyperpolarizabilities. The compounds were fully characterized by NMR, FTIR and UV/Vis spectroscopy and their electrochemical behaviour studied by cyclic voltammetry. Quadratic hyperpolarizabilities () were determined by hyper-Rayleigh scattering measurements at a fundamental wavelength of 1500 nm. Density functional theory calculations were employed to rationalize the second-order non-linear optical properties of these complexes.

Synthesis and characterization of COPPER(II) 4´-phenyl-terpyridine compounds and catalytic application for aerobic oxidation of benzylic alcohols

The reactions between 4'-phenyl-terpyridine (L) and nitrate, acetate or chloride Cu(II) salts led to the formation of [Cu(NO3)(2)L] (1), [Cu(OCOCH3)(2)L]center dot CH2Cl2 (2 center dot CH2Cl2)and [CuCl2L]center dot[Cu(Cl)(mu-Cl)L](2) (3), respectively. Upon dissolving 1 in mixtures of DMSO-MeOH or EtOH-DMF the compounds [Cu(H2O){OS(CH3)(2)}L]-(NO3)(2) (4) and [Cu(HO)(CH3CH2OH)L](NO3) (5) were obtained, in this order. Reaction of 3 with AgSO3CF3 led to [CuCl(OSO2CF3)L] (6). The compounds were characterized by ESI-MS, IR, elemental analysis, electrochemical techniques and, for 2-6, also by single crystal X-ray diffraction. They undergo, by cyclic voltammetry, two single-electron irreversible reductions assigned to Cu(II) -> Cu(I)and Cu(I) -> Cu(0) and, for those of the same structural type, the reduction potential appears to correlate with the summation of the values of the Lever electrochemical EL ligand parameter, which is reported for the first time for copper complexes. Complexes 1-6 in combination with TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl radical) can exhibit a high catalytic activity, under mild conditions and in alkaline aqueous solution, for the aerobic oxidation of benzylic alcohols. Molar yields up to 94% (based on the alcohol) with TON values up to 320 were achieved after 22 h.

Synthesis of organometallic Ruthenium(II) complexes with strong activity against several human canceer cell lines

A new family of "RuCp" (Cp=eta(5)-C5H5) derivatives with bidentate N,O and N,N'-heteroaromatic ligands revealed outstanding cytotoxic properties against several human cell lines namely, A2780, A2780CisR, HT29, MCF7, MDAMB231, and PD. IC50 values were much lower than those found for cisplatin. Crystal structure of compound 4 was determined by X-ray diffraction studies. Density functional theory (DFT) calculations performed for compound 1 showed electronic flow from the ruthenium center to the coordinated bidentate ligand, in agreement with the electrochemical studies and the existence of a metal-to-ligand charge-transfer (MLCT) band evidenced by spectroscopic data.

Synthesis and characterization of oxovanadium (IV) dithiocarbamates with pyridine

We report the synthesis and study of a new series of oxovanadium (IV) dithiocarbamate adducts and derivatives with pyridine and cyclohexyl, di-iso-butyl, di-n-propyl, anilin, morpholin, piperidin and di-iso-propyl amines. The complexes have been characterized by analytical, magnetochemical, IR, visible-UV spectral and thermal studies, and are assigned the formulas [VO(L)2].py, where L=cyclohexyl, di-iso-butyl, di-n-propyl, anilin dithiocarbamate and [VO(OH)(L)(py)2]OH.H2O (L=morpholin, piperidin and di-iso-propyl dithiocarbamate). The effect of the adduct formation on the pV=0 bound is discussed in terms of the IR (V=O, V-S and V-N stretching frequencies) and electronic spectra (d-d transitions).

Half-sandwich silane complexes of ruthenium and iron : synthesis, structure and application to catalysis

The present thesis describes syntheses, structural studies, and catalytic reactivity of new non-classical silane complexes of ruthenium and iron. The ruthenium complexes CpRu(PPri3)CI(T]2-HSiR3) (1) (SiR3 = SiCh (a), SiClzMe (b), SiCIMe2 (c), SiH2Ph (d), SiMe2Ph (e» were prepared by reactions of the new unsaturated complex CpRu(PPri3)CI with silanes. According to NMR studies and X-ray analyses, the complexes la-c exhibit unusual simultaneous Si··· H and Si··· CI-Ru interactions. The complex CpRu(PPri3)CI was also used for the preparation of the first examples of late transition metal agostic silylamido complexes CpRu(PPri3)(N(T]2-HSiMe2)R) (2) (R= Ar or But), which were characterized by NMR spectroscopy. The iron complexes CpFe(PMePri2)H2(SiR3) (3) (SiR3 = SiCh (a), SiClzMe (b), SiCIMe2 (c), SiH2Ph (d), SiMe2Ph (e» were synthesized by the reaction of the new borohydride iron complex CpFe(PMePri2)(B~) with silanes in the presence NEt3. The complexes 3 exhibit unprecedented two simultaneous and equivalent Si··· H interactions, which was confirmed by X-ray analyses and DFT calculations. A series of cationic ruthenium complexes [CpRu(PR3)(CH3CN)(112-HSiR'3)]BAF (PR3 = PPri 3 (4), PPh3 (5); SiR'3 = SiCh (a), SiClzMe (b), SiClMe2 (c), SiH2Ph (d), SiMe2Ph (e» was obtained by substitution of one of the labile acetonitrile ligands in [CpRu(PR3)(CH3CNh]BAF with sHanes. Analogous complexes [TpRu(PR3)(CH3CN)(T]2 -HSiR' 3)]BAF (5) were obtained by the reaction of TpRu(PR3)(CH3CN)CI with LiBAF in the presence of silanes. The complexes 4-5 were characterized by NMR spectroscopy, and the observed coupling constants J(Si-H) allowed us to estimate the extent of Si-H bond activation in these compounds. The catalytic activity in hydrosilylation reactions of all of the above complexes was examined. The most promising results were achieved with the cationic ruthenium precatalyst [CpRu(PPri3)(CH3CN)2t (6). Complex 6 shows good to excellent catalytic activity in the hydrosilylation of carbonyls, dehydrogenative coupling of silanes with alcohols, amines, acids, and reduction of acid chlorides. We also discovered very selective reduction of nitriles and pyridines into the corresponding N-silyl imines and l,4-dihydropyridines, respectively, at room temperature with the possibility of catalyst recycling. These chemoselective catalytic methods have no analogues in the literature. The reactions were proposed to proceed via an ionic mechanism with intermediate formation of the silane a-complexes 4.

POCN-type Pincer Complexes of NiII and NiIII : synthesis, reactivities, catalytic activities and physical properties

Cette thèse décrit la synthèse, la caractérisation, les réactivités, et les propriétés physiques de complexes divalents et trivalents de Ni formés à partir de nouveaux ligands «pincer» de type POCN. Les ligands POCN de type amine sont préparés d’une façon simple et efficace via l’amination réductrice de 3-hydroxybenzaldéhyde avec NaBH4 et plusieurs amines, suivie par la phosphination de l’amino alcool résultant pour installer la fonction phosphinite (OPR2); le ligand POCN de type imine 1,3-(i-Pr)2PC6H4C(H)=N(CH2Ph) est préparé de façon similaire en faisant usage de PhCH2NH2 en l’absence de NaBH4. La réaction de ces ligands «pincer» de type POCN avec NiBr2(CH3CN)x en présence d’une base résulte en un bon rendement de la cyclométalation du lien C-H situé en ortho aux fonctions amine et phosphinite. Il fut découvert que la base est essentielle pour la propreté et le haut rendement de la formation des complexes «pincer» désirés. Nous avons préparé des complexes «pincer» plan- carrés de type POCN, (POCNRR΄)NiBr, possédant des fonctions amines secondaires et tertiaires qui démontrent des réactivités différentes selon les substituants R et R΄. Par exemple, les complexes possédant des fonctions amines tertiaires ArCH2NR2 (NR2= NMe2, NEt2, and morpholinyl) démontrent des propriétés rédox intéressantes et pourraient être convertis en leurs analogues trivalents (POCNR2)NiBr2 lorsque réagis avec Br2 ou N-bromosuccinimide (NBS). Les complexes trivalents paramagnétiques à 17 électrons adoptent une géométrie de type plan-carré déformée, les atomes de Br occupant les positions axiale et équatoriale. Les analyses «DSC» et «TGA» des ces composés ont démontré qu’ils sont thermiquement stables jusqu’à ~170 °C; tandis que la spectroscopie d’absorption en solution a démontré qu’ils se décomposent thermiquement à beaucoup plus basse température pour regénérer les complexes divalents ne possédant qu’un seul Br; l’encombrement stérique des substitutants amines accélère cette route de décomposition de façon significative. Les analogues NMe2 et N(morpholinyl) de ces espèces de NiIII sont actifs pour catalyser la réaction d’addition de Kharasch, de CX4 à des oléfines telles que le styrène, tandis qu’il fut découvert que l’analogue le moins thermiquement stable (POCNEt2)Ni est complètement inerte pour catalyser cette réaction. Les complexes (POCNRH)NiBr possédant des fonctions amines secondaires permettent l’accès à des fonctions amines substituées de façon non symétrique via leur réaction avec des halogénures d’alkyle. Un autre avantage important de ces complexes réside dans la possibilité de déprotonation pour préparer des complexes POCN de type amide. De telles tentatives pour déprotoner les fonctions NRH nous ont permis de préparer des espèces dimériques possédant des ligands amides pontants. La nature dimérique des ces complexes [P,C,N,N-(2,6-(i-Pr)2PC6H3CH2NR)Ni]2 (R= PhCH2 et Ph) fut établie par des études de diffraction des rayons-X qui ont démontré différentes géométries pour les cœurs Ni2N2 selon le substituant N : l’analogue (PhCH2)N possède une orientation syn des substitutants benzyles et un arrangement ressemblant à celui du cyclobutane du Ni et des atomes d’azote, tandis que l’analogue PhN adopte un arrangement de type diamant quasi-planaire des atomes du Ni et des atomes d’azote et une orientation anti des substituants phényles. Les espèces dimériques ne se dissocient pas en présence d’alcools, mais elles promouvoient l’alcoolyse catalytique de l’acrylonitrile. De façon intéressante, les rendements de ces réactions sont plus élevés avec les alcools possédant des fonctions O-H plus acides, avec un nombre de «turnover» catalytique pouvant atteindre 2000 dans le cas de m-cresol. Nous croyons que ces réactions d’alcoolyse procèdent par activation hétérolytique de l’alcool par l’espèce dimérique via des liaisons hydrogènes avec une ou deux des fonctions amides du dimère. Les espèces dimériques de Ni (II) s’oxydent facilement électrochimiquement et par reaction avec NBS ou Br2. De façon surprenante, l’oxydation chimique mène à l’isolation de nouveaux produits monomériques dans lesquels le centre métallique et le ligand sont oxydés. Le mécanisme d’oxydation fut aussi investigué par RMN, «UV-vis-NIR», «DFT» et spectroélectrochimie.