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Phosphane and Phosphite Silver(I) Complexes: Synthesis, Reaction Chemistry and their Use as CVD PrecursorsDjiele Ngameni, Patrice 27 January 2005 (has links)
Silver(I) complexes of type LnAgX (X = organic ligand, such as carboxylates, dicarboxylates, Schiff-base; L = Lewis-bases, e. g. PnBu3, P(OMe)3, P(OEt)3; n = 1, 2, 3) have been synthesized and characterized with respect to their suitability for the Chemical Vapour Deposition (CVD) of silver thin films. For some of these compounds single crystal could be obtained. Their solid-state structure was determined by single crystal X-ray diffraction. The volatility, thermal stability, and gas phase decomposition mechanism of selected compounds were studied using temperature-programmed and in-situ mass spectrometry. CVD experiments were performed according to the results of the gas phase analysis. Silver films could be grown by using a cold-wall CVD reactor. The morphology of the latter films was determined. / Silber(I) Komplexe LnAgX (X = organische Ligand, Z. B. Carboxylate, Dicarboxylate, Schiff Base; L = Lewis-Base, Z. B. PnBu3, P(OMe)3, P(OEt)3; n = 1, 2, 3) wurden Bezug auf ihre Eignung für die chemische Gasphasenabscheidung von Silberfilmen synthetisiert und charakterisiert. Von einigen dieser Verbindung konnten Einkristalle erhalten werden. Der Bau dieser Verbindungen wurde mittels Röntgeneinkristallographie ermittelt. Ausgewählten Verbindungen wurden mit Temperatur-programmierter und in-situ Massenspektrometrie analysiert. Gasphasenabscheidungs- mechanismen für einige Prekursoren sind vorgestellt. CVD-Abscheidungsexperimente wurden entsprechend den Ergebnissen der Gasphaseanalyse durchgeführt. Silber Schichten konnten mit einen Kaltwand CVD-Reaktor erzeugt werden, deren Oberflächenmorphologie wurde untersucht.
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Nitrogen-enriched hierarchically porous carbon materials fabricated by graphene aerogel templated Schiff-base chemistry for high performance electrochemical capacitorsYang, Xiangwen, Zhuang, Xiaodong, Huang, Yinjuan, Jiang, Jianzhong, Tian, Hao, Wu, Dongqing, Zhang, Fan, Mai, Yiyong, Feng, Xinliang 16 December 2019 (has links)
This article presents a facile and effective approach for synthesizing three-dimensional (3D) graphenecoupled Schiff-base hierarchically porous polymers (GS-HPPs). The method involves the polymerization of melamine and 1,4-phthalaldehyde, yielding Schiff-base porous polymers on the interconnected macroporous frameworks of 3D graphene aerogels. The as-synthesized GS-HPPs possess hierarchically porous structures containing macro-/meso-/micropores, along with large specific surface areas up to 776 m² g⁻¹ and high nitrogen contents up to 36.8 wt%. Consequently, 3D nitrogen-enriched hierarchically porous carbon (N-HPC) materials with macro-/meso-/micropores were obtained by the pyrolysis of the GS-HPPs at a high temperature of
800 °C under a nitrogen atmosphere. With a hierarchically porous structure, good thermal stability and a high nitrogen-doping content up to 7.2 wt%, the N-HPC samples show a high specific capacitance of 335 F g⁻¹ at 0.1 A g⁻¹ in 6 M KOH, a good capacitance retention with increasing current density, and an outstanding cycling stability. The superior electrochemical performance means that the N-HPC materials have great potential as electrode materials for supercapacitors.
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Koordinationsverbindungen von Schiff-Basen des 3-Aminopropyltriethoxysilans und 3-(2-Aminoethylamino)-propyl-trimethoxysilans mit α-Hydroxybenzocarbonyl-VerbindungenEfendi, Jon 17 March 2003 (has links)
Die vorliegende Arbeit befasst sich mit Untersuchungen zur Komplexbildung von Cu2+, Zn2+, sowie Sn2+ und B(OMe)3 mit den Schiff-Basen aus 3-Aminopropyl-triethoxysilan (APTES) und 3-(2-Aminoethyl-amino)-propyl-trimethoxysilan (AEPTMS) mit α-Hydroxybenzocarbonylverbindungen. Die Liganden und die Komplexe wurden mit IR-, UV/VIS- und NMR-Spektroskopie charakterisiert. IR-Untersuchungen zeigen die charakteristischen C=N- und C=O-Valenzschwingungen. Sie werden durch die Komplexbildung deutlich verschoben. Die 1H- und 13C-NMR-Messungen indizieren die Komplexbildung mit einer signifikanten Verschiebung in den Signallagen der H- und C-Nachbaratome der Donatoratome. 29Si-NMR-Messungen indizieren keine Hydrolyse- und Kondensationsreaktionen im Verlauf der Synthese. Bei der Komplex-Synthese mit wasserhaltigen Übergangsmetallsalzen wurden Produkte von Sol-Gel-Prozessen gefunden. UV/VIS-spektroskopische Untersuchungen an den Mischungen der Übergangsmetallsalze mit APTES bzw. AEPTMS zeigen die Bildung typischer Aminkomplexe.
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Monomeric, Dimeric and Polymeric Re<sup>I</sup>(CO)<sub>3</sub> Schiff Base Complexes: Synthetic, Spectroscopic, Electrochemical, and Computational StudiesHasheminasab, S. Abed 09 June 2016 (has links)
No description available.
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Neuartige Pyrrol/Pyrazol-Bausteine für die Synthese von Hybrid-Makrozyklen, azyklischen Ligandsystemen und bimetallischen Komplexen / Novel Pyrrole/Pyrazole-building blocks for the synthesis of Hybrid-Macrocycles, acyclic ligand systems and bimetallic complexesKatsiaouni, Stamatia 01 November 2007 (has links)
No description available.
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Höherkoordinierte Komplexverbindungen des Siliciums, Germaniums und Zinns mit chiralen O,N,O´-LigandenFels, Sabine 09 September 2016 (has links)
Aufgrund ihrer Eigenschaften und möglicher Anwendungen werden Siliciumkomplexe mit O,N,O´-Ligandsystemen in der Literatur beschrieben. Jedoch fehlen bisher Untersuchungen zur Strukturaufklärung. Im Rahmen dieser Arbeit wurden zahlreiche Silicium-, Germanium- und Zinnkomplexe mit chiralen O,N,O´-Liganden synthetisiert und strukturanalytisch charakterisiert. Dazu wurden die Liganden durch Kondensationsreaktionen von enantiomerenreinen Aminosäuren mit aromatischen ortho-Hydroxyaldehyden bzw. Acetylaceton hergestellt. Die weitere Umsetzung der Liganden mit Elementhalogeniden der Gruppe 14 führte zu den angestrebten Komplexverbindungen. Alle hergestellten Verbindungen wurden umfassend charakterisiert (NMR-, UV/Vis-, IR-Spektroskopie, Elementaranalyse, Einkristallstrukturanalyse, Drehwert). Quantenchemische Berechnungen an einfachen Modellverbindungen sowie an hergestellten Silicium- und Zinnkomplexen führten zu einem grundlegenden Verständnis der Festkörper-NMR-Parameter dieser Verbindungsklasse.
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Serendipitous Assembly Of 3d Metal-Ion Polyclusters : Structures, Magnetic Behavior And Theoretical StudiesMukherjee, Sandip 07 1900 (has links) (PDF)
The last two decades have seen extensive growth in interest in metal-ion assemblies, especially for building new polynuclear exchange-coupled magnetic systems. However, the concept of designing polynuclear extended structures has still not matured to the level of retro-synthetic approach developed for the organic and pharmacological molecules. Although some progress has been made with secondary building units (SBUs) in metal-organic-frameworks (MOFs), the control seems to be just an illusion when it comes to bridging ligands such as the azide ion. When it is asserted that the azido ligand is versatile in its bridging capabilities, what is actually meant is that it would be difficult to predict or control its bridging properties, or in other words, the azido based polynuclear complexes are difficult to pre-design. However, this kind of serendipity is not always bad news for the chemists. For example, the azido ligand has been shown to mediate magnetic exchanges between paramagnetic metals in a predictable fashion (usually depending upon the bonding geometries). Therefore, it is a well-respected ligand in polynuclear assemblies of paramagnetic ions. Serendipitous assemblies offer new magnetic structures that we may not otherwise even think about synthesizing. Similarly, there are other ligands, such as alkoxido, oximato, carboxylato etc. which also behave like azide. These ligands are very important in the study of magnetic exchanges to develop an understanding of the underlying mechanisms in molecular magnetism. Serendipitous assemblies have also led to systems like single molecule magnets (SMMs), which have enriched the field with potential applications in computing and have also been used for the confirmation of the quantum magnetic properties like tunneling phenomenon, spin decoherence etc.
Investigations incorporated in this thesis work led to several novel strategies for using serendipity as an advantage and build unprecedented structural topologies with interesting new molecular-magnetic properties. All the reported complexes were thoroughly analyzed through elemental analysis, spectroscopy, X-ray structure determination (both single crystal & powder diffractions) and variable temperature magnetic susceptibility measurements. In a few suitable cases, model structures obtained from the X-ray structures were also employed to study the magnetic exchange mechanisms through density functional theory (DFT) calculations and simulations.
CHAPTER 1 of the thesis presents a general review on the ever-growing field of metal-ion assembly. In particular, the importance of the ‘serendipitous approach’ to build new and interesting metal-ion clusters and polyclusters is highlighted. This chapter also describes the basic concepts of exchange-based molecular magnetism as applied to the metal-ion assemblies.
CHAPTER 2 describes the concept of using lower molar proportions of blocking bidentate chelating ligands in the neutral copper(II)-azido systems, which increases the number of coordination sites for the versatile azido bridges to assemble the metal-ions in higher dimensions, based on smaller cluster units. Syntheses, structures and magnetic properties of ten novel complexes are described in this chapter: [Cu3(tmen)2(N3)6]n (1), [Cu4(Me-hmpz)2(N3)8]n (2), [Cu4(men)2(N3)8]n (3), [Cu6(deen)2(N3)12]n (4), [Cu6(aem)2(N3)12]n (5), [Cu6(dmeen)2(H2O)2(N3)12]n (6), [Cu6(N,N'-dmen)2(N3)12]n (7), [Cu6(hmpz)2(N3)12]n (8), Cu5(N,N-dmen)2(N3)10]n (9), and [Cu5(N,N'-dmen)5(N3)10]n (10) [tmen = N,N,N',N'-tetramethylethylenediamine, Me-hmpz = 1-methylhomopiperazine, men = N-methylethylenediamine, deen = N,N'-diethylethylenediamine, aem = 4-(2-aminoethyl)morpholine, dmeen = N,N-dimethyl-N'-ethylethylenediamine, N,N'-dmen = N,N'-dimethylethylenediamine, hmpz = homopiperazine, N,N-dmen = N,N-dimethylethylenediamine].
Most of these complexes have simple oligonuclear basic building units (Scheme 1), such as trinuclear (1), tetranuclear (2, 3) and hexanuclear (4-8), but the overall arrangements of these cluster units in higher dimensions vary widely and serendipitously. For example, the hexanuclear complexes 4-7, although having almost identical basic structures, assemble in three- (4, 5) or two- (6, 7) dimensions with different connectivity among the basic structures. However, complex
9 is made from two different building units (Cu2 and Cu3). Complex 10, although having metal to blocking molar ratio 1:1, presents an unprecedented 1D structure for such complexes. Analysis of the magnetic susceptibility data for complexes 1-9 using theoretical exchange models for fitting is also described. Density functional theory (DFT, B3LYP) was employed to further analyze the experimental magnetic data for complexes 1, 2, 3 and 9 to better understand the magnetic exchange mechanisms in such systems.
CHAPTER 3 continues with the same concepts developed in the previous chapter using multidentate neutral and anionic co-ligands. Using lower molar proportions of these multidentate ligands, seven novel complexes have been synthesized (keeping the initial metal to ligand ratio as 2:1): [Cu4(L1)2(N3)8]n (11), [Cu4(L2)2(N3)8]n (12), [Cu4(L3)2(N3)8]n (13), [Cu4(L4)2(N3)8]n (14), [Cu9(L5)4(N3)18]n (15), [Cu4(L6)2(H2O)2(N3)6] (16) and [Cu4(L7)2(N3)6]n (17) [where L1-5 are the condensation products of 2-pyridinecarboxaldehyde and 2-{2-(methylamino)ethyl}pyridine (L1),
N,N-diethylethylenediamine (L2), N,N-dimethylethylenediamine (L3), N-methylethylenediamine (L4), N,N,2,2-tetramethylpropanediamine (L5); HL6 and HL7 are the condensation products of 2-hydroxy-3-methoxybenzaldehyde with N,N-diethylethylenediamine (HL6), and N-ethylethylenediamine (HL7)]. The ligand L1 is particularly interesting, as it is a hemiaminal ether (usually considered to be unstable intermediates in the reactions of aldehydes and secondary amines in alcoholic solvents), and was found to be trapped in 11. Although 11-13 have identical tetranuclear basic structures (with the rare simultaneous end-on and end-to-end bridges between two neighbouring metal-ions, Scheme 2) and extend in one-dimension. However, 13 is differently organized from the other two complexes. For 14, the bridging structure among the peripheral copper(II) ions changes to double end-on (Scheme 2), and the resulting structure extends in two dimensions. However, with L5, metal to ligand ratio is 9:4 (under similar conditions and initial molar proportions of the components) in 15, which can be seen as two different fragments: [Cu4(L5)4(N3)6]2+ and [Cu5(N3)12]2- linked alternately to give an overall 1D structure. HL6 and HL7 have one ionisable phenolic group that replaces one azido anion and generates two pockets for the metal atoms. These monoanionic ligands give tetranuclear complexes (16 and 17) with basic structures resembling (Scheme 2) to 11-14. While 17 is 1D in nature, two coordinated water molecules prevent the structure of 16 to grow and results in a discrete cluster.
The variable temperature magnetic properties of these complexes were thoroughly analyzed through experimental and theoretical (DFT) studies.
CHAPTER 4 reports the use of a pyridyl substituted propanediolate ligand in the assembly of two novel 1D heterometallic complexes: [Mn3Na(L)4(CH3CO2)(MeOH)2](ClO4)2∙3H2O (18) and [Mn3Na(L)4(CH3CH2CO2)(MeOH)2](ClO4)2∙2MeOH∙H2O (19) [LH2 = 2-methyl-2-(2-pyridyl)propane-1,3-diol, Scheme 3]; both featuring octahedral MnIV ions linked alternately to one trigonal prismatic MnII ion and even more interestingly to one trigonal prismatic NaI ion (Scheme 3). The complexes are essentially identical in structure and magnetic behavior, showing a weak ferromagnetic interaction among the neighboring manganese ions. DFT studies on a model complex supports the S = 11/2 ground spin state, deduced from dc and ac susceptibility measurements.
CHAPTER 5 illustrates the use of a few dicarboxylates as potential bridging ligands to assemble tri- and hexanuclear MnIII-clusters. With the salicylaldoximate (salox) as the [MnIII3O(salox)3]+, triangle-generating moiety and keeping the reaction conditions (solvent, base, reaction time and crystallization process) identical, four new extended complexes that differ both in their basic and higher dimensional organizations are reported. When 1,3-phenylenediacetate (phda) is used (in EtOH), in the resulting complex [MnIII6O2(salox)6(EtOH)4(phda)]n∙(saloxH2)n∙(2H2O)n (20), a single type of MnIII6 clusters are linked by the dicarboxylate (interestingly the complex crystallizes with uncoordinated saloxH2 molecules). However, when two differently substituted isophthalate linkers (5-iodoisophthalate and 5-azidoisophthalate) are used, two almost identical complexes [MnIII6O2(salox)6(MeOH)5(5-I-isoph)]n∙(3MeOH)n (21) and [MnIII6O2(salox)6(MeOH)4(H2O)(5-N3-isoph)]n∙(4MeOH)n (22) are isolated, with two different types of Mn6 clusters (Scheme 4) linked alternately in one dimension. More interestingly, use of another substituted isophthalate (5-nitroisophthalate) produced a heteronuclear complex [MnIII3NaO(salox)3(MeOH)4(5-NO2-isoph)]n∙(MeOH)n(H2O)n (23) with only MnIII3 triangles as the basic cluster assembled in two dimensions. Temperature and field dependent dc and ac susceptibility measurements show that the complexes 20-22 behave as non-interacting single molecule magnets with ground spin state S = 4. Complex 23 is dominantly antiferromagnetic with a ground spin state S = 2. The magnetic behaviours of these complexes are also supported by theoretical calculations (DFT) on models generated from the crystal structures.
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Ligands Phosphine-diène et Salicylamidines : chimie de coordination, catalyse et thérapie / Phosphine-diène and Salicylamidines ligands : coordination chemistry, catalysis and therapyChotard, Florian 29 September 2017 (has links)
Les travaux de thèse retranscrits dans ce mémoire ont pour sujet l’élaboration de nouveaux ligands pour la coordination de métaux et l’application des complexes correspondants pour la catalyse et la thérapie.La première partie du manuscrit traite de l’élaboration de ligands phosphine-diène, de leurs analogues saturés et des complexes arène-ruthénium correspondants. Le départ d’arène permet au ligand phosphine-cycloheptadiène de former avec le ruthénium un complexe bimétallique cationique où le ligand est chélate κ-P/diène-η4. Ces complexes ont été appliqués en catalyse pour l’addition radicalaire par transfert d’atome (ATRA) de CCl4 au styrène. Lors de l’utilisation de conditions dures, la supériorité des complexes « diène » a pu être mise en évidence par rapport aux analogues saturés.La seconde partie rapporte le développement de nouveaux analogues de base de Schiff : les « salicylamidines ». L’utilisation de différentes voies de synthèse a permis d’obtenir plusieurs générations de ligands. Ils ont été utilisés pour la coordination de métaux et sont particulièrement adaptés à la formation de complexes avec le zinc et l’aluminium. Certains de ces composés ont été utilisés pour la polymérisation par ouverture de cycle (ROP) de lactides et ont démontré une bonne activité.La dernière partie concerne la synthèse et l’évaluation de complexes métalliques comme agents anticancéreux. Des complexes phosphine-or et phosphine-ruthénium ont été synthétisés et évalués pour leur activité antiproliférative. Les complexes phosphine-or présentent une activité remarquable, meilleure que le cisplatine. La nature de l’arène des complexes phosphine-ruthénium influe fortement sur leur activité, les dérivés « benzoate d’éthyle » donnent des cytotoxicités significativement meilleures que les analogues « p-cymène ». Des complexes de titane et de zirconium avec un ligand de type aza-dipyrrométhène ont été synthétisés. Une étude préliminaire de leurs propriétés photophysiques a été réalisée et a indiqué que les composés étaient fluorescents. L’étude de leur propriété anticancéreuse a démontré une faible cytotoxicité. / The subject of this thesis concerns the development of new ligands, their coordination chemistry, and the synthesis of the corresponding metal complexes for catalysis and therapy.The first part of this work relates to the synthesis of diene-phosphine ligands, their saturated analogs, and the corresponding arene-ruthenium complexes. Arene decoordination allows the formation of a cationic bimetallic complex where the ligand is diène-η4/κ-P coordinated to the ruthenium. These complexes have been applied to atom transfer radical addition (ATRA) of CCl4 to styrene. When harsh reaction conditions are used, the superiority of the “diene” complexes is highlighted comparing to saturated analogs.The second part concerns the development of new Schiff base analogs: the “salicylamidines”. Several ligand generations have been obtained following different synthetic paths. They have been used for metal coordination, and are especially well-suited for the formation of zinc and aluminium complexes. Some of the compounds have been applied to ring opening polymerization (ROP) of lactides, and demonstrated good activity.The last part reports on the synthesis and assessment of metal-based anticancer agents. Some phosphine-gold and phosphine-ruthenium complexes have been synthesized and tested for their antiproliferative activity on several cancer cell lines. The phosphine-gold complexes showed impressive activities, better than cisplatine. Activity of phosphine-ruthenium is strongly influenced by the nature of the arene, ethyl benzoate derivatives are significantly more cytotoxic than p-cymene ones. Titanium and zirconium complexes with aza-dipyrromethene ligand were synthesized. Preliminary photophysical study was performed and indicated fluorescence. Their anticancer properties were assessed, and they are only poorly cytotoxic.
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Le Gossypol et ses nouveaux dérivés:Synthèse et étude d'Activités BiologiquesDAO, VI THUY 11 December 2002 (has links) (PDF)
Plusieurs molécules nouvelles ont été obtenues à partir du Gossypol, extrait des graines de cotonnier. Dans la première partie, de nouvelles bases de Schiff du gossypol et de la gossypolone ont été synthétisées, les énantiomères du gossypol et leurs bases de Schiff sont optiquement stables, tandis que, les énantiomères de la gossypolone ne sont pas stables à température ambiante, mais il est possible de les observer vers 0°C. La cytotoxicité de ces bases de Schiff a été évaluée principalement sur des cellules KB, la méthylimine et l'éthylimine de la gossypolone sont les plus toxiques (IC50= 0.8 et 1.2 µM). La toxicité du gossypol et de la gossypolone augmente quand les tests sont effectués en absence de sérum et elle diminue en présence de catalase ou de mannitol dans le milieu de culture. L'énantiomère (-)-gossypol est plus toxique que le (+)-gossypol, ceci est aussi valable pour les bases de Schiff des énantiomères du gossypol. Dans la deuxième partie, une nouvelle classe de dérivés du gossypol et de la gossypolone, les dithianes et les dithiolanes, a été développée. Les dithianes/dithiolanes du gossypol et de la gossypolone ont été synthétisés par action de dithiols en présence d'éthérate de trifluoroborate. La même réaction effectuée avec les monothiols, conduit à des mélanges complexes. L'action du propanedithiol ou de l'ethanedithiol sur le tetraméthyle ou l'hexaméthyle éthers du gossypol ne conduit pas aux dithianes ou dithiolanes attendus mais à de nouveaux dérivés cycliques. La toxicité de ces nouveaux thio-dérivés sur les cellules KB est assez modeste, mais sous l'action de NO ou d'un sel de nitrosonium, ces dérivés se transforment en dérivés plus toxiques dans le cas du gossypol ou régénèrent la molécule de départ dans le cas de la gossypolone. Nous formulons l'hypothèse que dithianes et dithiolanes du gossypol et de la gossypolone pourraient être des modèles de prodrogues ciblées sur les cellules exprimant de fortes concentrations d'oxyde nitrique.
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Metallo-supramolecular Architectures based on Multifunctional N-Donor LigandsTanh Jeazet, Harold Brice 18 August 2010 (has links) (PDF)
Self-assembly processes were used to construct supramolecular architectures based on metal-ligand interactions. The structures formed strongly depend on the used metal ion, the ligand type, the chosen counter ion and solvent as well as on the experimental conditions. The focus of the studies was the design of multifunctional N-donor ligands and the characterization of their complexing and structural properties. This work was divided into three distinct main parts: The bis(2-pyridylimine), the bis(2-hydroxyaryl) imine and the tripodal imine / amine ligand approach.
In the first part a series of bis(2-pyridylimine) derivatives having different linking elements were employed as building blocks for novel supramolecular architectures. Reaction of individual d-block metal salts with these ligands has led to the isolation of coordination polymers, a metallamacrocycle, double-stranded helicates, triple-stranded helicates as well as of circular meso-helicates. The nature of the spacer in the Schiff base ligands, the noncovalent weak interactions, such as hydrogen bond, face-to-face π-π and edge-to-face CH-π interactions, are all important factors influencing the architecture of the final products.
Topological control of the assembly process of the hexanuclear meso-helicates is clearly associated with the bidentate coordination of the sulfate anion which directs the formation of a double- rather than a triple-stranded helicate around the octahedrally coordinated Cu(II). Surprisingly, the variation of the linker function in the ligands, which significantly changes the linking angle of the pyridylimine strands, has only a little influence of the resulting structure. Also the use of a mixture of ligands does not influence the meso-helicate topology; the result is the symmetrically mixed meso-helicate.
The new iron(II) triple helicate [Fe2(L5)3](PF6)4 14 {L5 = bis[4-(2-pyridylmethyleneimino)phenyl]-1,1-cyclohexane} in its chloride form binds strongly to DNA as confirmed by induced circular dichroism signals in both the metal-to-ligand charge transfer (MLCT) and in-ligand bands of the helicate. The induced CD spectrum gives some evidence that [Fe2(L5)3]4+ interacts with the DNA in a single binding mode, which is consistent with major groove binding.
The cytotoxicity of the new iron(II) triple helicate 14 was evaluated on human lung cancer A549 cells and compared with that of cisplatin and that of the previously reported iron(II) triple helicate [Fe2(L1)3]4+{L1 = bis[4-(2-pyridylmethyleneimino)phenyl]methane}. The first results show some distinguishing features for 14 obviously caused by the existing structural differences of the complexes.
In the second part of the thesis, novel uranyl complexes of the bis(2-hydroxyaryl) imine ligands have been synthesized and characterized. 1D coordination polymers and mononuclear structures were formed. In all complexes a distorted hexagonal bipyramidal coordination geometry around the uranyl centre is observed. The imine nitrogen atoms of the ligands do not bind to the metal centre but interact strongly with the hydroxy group via H-bonding. DFT calculations made with L8 ( α,α’-Bis(salicylimino)-m-xylene) are in good agreement with the X-ray crystal structure data. Liquid-liquid extraction studies involving selected ligands and Eu(III) or U(VI) indicate remarkably high selectivity for U(VI) over Eu(III) at weak acidic pH conditions. We believe that the study made opens up new possibilities for uranyl ion extraction which could be interesting in view of the treatment of nuclear waste.
In the third part of the thesis, a series of multifunctional tripodal ligands with different N-donor centres were used for U(VI) and lanthanide, Nd(III), Eu(III) and Yb(III), binding and extraction. Reaction of these metal ions with selected tripodal ligands afforded complexes which were characterized by ESI mass spectroscopy. The complex composition was found to be 1:1 in all cases. The extraction behaviour of the tripodal ligands towards Eu(III) and U(VI) was studied both in the absence and presence of octanoic acid as co-ligand using the extraction system Eu(NO3)3 or UO2(NO3)2–buffer–H2O/ ligand–CHCl3. These separation systems show a remarkably high selectivity for U(VI) over Eu(III). It is interesting to note that the addition of the octanoic acid to the extraction system leads to high synergistic effects. A series of Eu(III) extraction experiments were done to clarify the composition of the extracted complexes. The results clearly point to the formation of various species with changing composition.
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