Analogues structuraux des porphyrines et des Salens, des ligands de type dipyrrométhène bis-phénol ont été étudiés dans notre groupe, notamment sous forme de complexes pour la catalyse d'oxydation. L'activité catalytique de ces complexes étant faible, il a été proposé de remplacer les phénols par des triazoles. L'objet de cette thèse était d'étudier et de valoriser une nouvelle famille de ligands dipyrrométhène bis-triazole.Plusieurs voies de synthèse ont d'abord été étudiées et optimisées pour accéder à ces nouveaux ligands. Nous nous sommes attachés ensuite à valoriser ces nouveaux ligands selon plusieurs axes.Un de ces ligands a été testé en reconnaissance d'anions, ainsi que les dérivés monotriazolium et bis-triazolium. Les triazoliums ont également permis l'accès à des métallocomplexes carbéniques, qui ont été étudiés.Par ailleurs, les métallocomplexes des dipyrrométhène bis-triazole ont été préparés et caractérisés, y compris par électrochimie. Des essais d'utilisation en oxydation ont été entrepris. Enfin, la synthèse de BODIPYs® liposolubles et hydrosolubles a été réalisée. Les propriétés optiques ont été mesurées puis ces dérivés fluorescents ont été testés pour le marquage fluorescent de cellules HeLa / Known as structural analogues of porphyrins and Salens, dipyrromethene bis-phenol-type ligands have been studied in our group, especially as complexes for oxidation catalysis. Due to the poor catalytic activity of these complexes, it has been proposed to replace the phenol moieties with triazoles. The purpose of this thesis was to study and develop a new family of dipyrromethene bis-triazole ligands.Several synthetic routes were first investigated and optimized to reach these new ligands. We then have endeavoured to add value to these new ligands along several lines.The ligand has been tested in anion recognition, as well as monotriazolium and bis-triazolium derivatives. The triazoliums also allowed access to carbene metallocomplexes that were studied.Furthermore, dipyrromethene bis-triazole metallocomplexes were prepared and characterized, notably by electrochemistry. Oxidation catalysis tests were undertaken.Finally, the synthesis of liposoluble and hydrosoluble BODIPYs® was performed. Their optical properties were measured and these fluorescent derivatives were tested for the fluorescent labeling of HeLa cells

Abstract not available

For the purpose of incorporating indoles into organometallic complexes for catalysis, as well as in the generation of new heterocyclic systems, various reactions have been carried out at C2, C6 and C7 of the indole system. In order to achieve this, 3-substituted 4,6-dimethoxyindoles and 6-hydroxy- 4-methoxyindoles were necessary as starting materials. Consequently, a lithium-bromide-templated one-pot procedure for the synthesis of some 3-substituted 4,6-dimethoxyindoles and a selective demethylation procedure for 3-substituted 6-hydroxy-4-methoxyindoles were developed. Various kinds of novel methylene-bridged bi-, tri-, and tetradentate pyridyl-indole ligands were synthesised via Vilsmeier-Haack, Friedel-Crafts or electrophilic addition reactions on the indole heterocycle. However, their metal complexing properties were generally weak and variable. Nevertheless, some of the tridentate pyridylindole ligands showed strong anion binding to halides, whereas a remarkable ligand transformation occurred with a bidentate 2-pyridylindole ligand and zinc(II), giving a substituted indolo[2,3-c]pyrrolo-[3,2,1-ij]quinoline system. Two new types of tetradentate Schiff base ligands were prepared from 2-formyl-indoles and 7-formyl-6-hydroxyindoles, and diamines. These preformed ligands were reacted with first- and second-row transition metals to give neutral metal complexes. Novel heterocyclic systems such as 4H-pyrrolo[3,2,1-ij]quinolines, 3H-pyrrolo-[1,2-a]indoles, and 1H-furo[2,3-g]indoles were synthesised from 2-formyl-, 7-formyl-, and 6-hydroxyindoles, utilising mainly intra-molecular Wittig reactions, Claisen-Schmidt condensations or acid- and base-catalysed cyclisations. A common feature of the prepared 4H-pyrrolo[3,2,1-ij]quinolines and 3H-pyrrolo-[1,2-a]indoles was their intense fluorescent character, which was examined as well.

[Truncated abstract] Chapter 1 provides an introduction to the 'sarcophagine' class of ligands and the field of metallopolymers. The synthesis, stereochemistry, physical properties and functionalisation of 'sarcophagines' and their metal complexes are discussed. A brief overview of the burgeoning field of metallopolymers is given with specific mention of the synthetic routes to pendant metallopolymers, and how these could be employed to prepared cage amine containing metallopolymers. Chapter 2 deals with the synthesis, characterisation and reactivity of cinnamylamino and styrylamido derivatives of the cage amines [Co((NH2)2sar)]3+, [Co((CH3)(NH2)sar)]3+ and [Cu((NH2)2sar)]2+. The cinnamylamino derivatives were prepared using reductive alkylation of the aforementioned amines with cinnamaldehyde. Procedures were developed to isolate the complexes without causing unwanted additions to the double bond. The cinnamylamino derivatives displayed unexpected reactivity towards a range of reducing agents, resulting in unexpected reduction of the double bond and cleavage of the cinnamyl group, but ultimately in the preparation of phenylpropylamino derivatives of [Co((NH2)2sar)]3+ and [Co((CH3)(NH2)sar)]3+. Attempts to rationalise the reactivity of the double bond have been explored based upon the physical properties and reactivity of the double bond. The styrylamido derivatives were prepared by treatment of the cage amines with 4-vinylbenzoyl chloride, and the complexes isolated in a similar manner to those of the cinnamylamino derivatives to ensure the amide linkage remained intact. Most of the complexes have been structurally characterised. ... Both the 2-thienyl and 3-thienyl derivatives of [Co((NH2)2sar)]3+ and [Co((CH3)(NH2)sar)]3+ have been prepared using reductive alkylation with the respective carboxaldehydes of thiophene. One of the optically pure isomers has been prepared. The complexes have been fully characterised including structural characterisation. Polymerisation of the thiophene-cage amine complexes was investigated under a range of chemical and electrochemical conditions, though polymerisation was never observed. Cleavage of the thienyl groups was observed when ceric ammonium nitrate in nitric acid was used as the oxidant. The attachment of oligothiophenes and mixed pyrrole-thiophene oligomers to cage amines were investigated using reductive alkylation and various pyrrole ring-forming reactions about the apical amino groups, though none of the desired complexes were isolated, reasons for the lack of reactivity were discussed. An efficient synthesis of N-(4-benzoic acid)- 2,5-di(2-thienyl)pyrrole was developed and was shown to the electropolymerisable, albeit the polymer films were non-conducting. Attempts to couple N-(4-benzoic acid)- 2,5-di(2-thienyl)pyrrole with a cage amine via its acid chloride were complicated by decomposition reactions, the nature of one of these products is discussed. Chapter 5 presents investigations into the preparation of simple complexes containing multiple cage amines using alkylation and acylation procedures with aromatic substrates. The complexes were found to exhibit some interesting electrochemical and chemical properties, demonstrating that even simple multiple cage amine species can display complicated and interesting behaviour.

This thesis describes the investigation of the coordination and supramolecular chemistry of three different types of pyridine-containing ligand with a selection of Ag(I), Cu(I), Cu(II) and Cd(II) salts. The ligand types are flexible and four-armed, rigid and four-armed and bent with two rigid arms. All the ligands also display the ability to form additional supramolecular interactions. Chapter one introduces supramolecular chemistry and crystal engineering and covers background on several areas of current interest in these fields. Network structures, both coordination polymers and hydrogen-bonded systems, are discussed and topological analysis as a method of describing and comparing network structures is introduced. An outline of the ligand design, choice of transition metals and anions is given. Chapter two provides a review of flexible four-armed pyridine-containing ligands and their use in coordination chemistry. The synthesis and characterisation of three flexible four-armed ligands 1,2,4,5-tetrakis(2-pyridylmethyl-sulfanylmethyl)benzene (2tet), 1,2,4,5-tetrakis(3-pyridylmethyl-sulfanylmethyl)benzene (3tet) and 1,2,4,5-tetrakis(4-pyridylmethyl-sulfanylmethyl)benzene (4tet) are given. The synthesis and characterisation of the Ag(I), Cu(II) and Cd(II) complexes formed with these three ligands are also given. The complex of [Cd(2tet)(NO₃)₄] was structurally characterised by X-ray diffraction and was found to be a discrete species. The complexes {[Ag₂(3tet)](ClO₄)₂}n̲, {[Ag₂(3tet)](PF₆)₂}n̲, {[Ag₂(3tet)](CF₃CO₂)₂}n̲, {[Ag₂(4tet)]-(ClO₄)₂�2MeCN�2CHCl₃}n̲, {[Ag₂(4tet)](PF₆)₂�6MeCN}n̲ and {[Ag₂(4tet)](ClO₄)₂-�3H₂O}n̲ were likewise structurally characterised by X-ray diffraction. All these complexes were three-dimensional coordination polymers. A comparison of the seven structures is given at the end of the chapter. Chapter three reviews rigid four-armed pyridine-containing ligands and their use in coordination chemistry. The preparation of the rigid four-armed ligand 2,3,4,5-tetrakis(4-pyridyl)thiophene (pyth) is given. The synthesis and characterisation of the Ag(I), Cu(I) and Cd(II) complexes formed with this ligand are also given. The complexes [Ag(pyth)](BF₄)�3MeCN�CH₂Cl₂}n̲, [Ag(pyth)](PF₆)�MeCN�CH₂Cl₂}n̲, [Ag(pyth)]-(CF₃SO₃)�2MeCN�CH₂Cl₂}n̲, [Cu(pyth)](PF₆)�MeCN�CH₂Cl₂}n̲ and [(Cu₂I₂)(pyth)]-(BF₄)�1/2CH₂Cl₂�H₂O}n̲ were structurally characterised by X-ray diffraction. The complex with CuI was a two-dimensional coordination polymer, and the other four complexes were three-dimensional coordination polymers. A comparison of the five structures is given at the end of the chapter. Chapter four begins with a review of rigid angular bridging ligands and their use in coordination and supramolecular chemistry. The preparation of the ligand bis(4-pyridyl)amine (bpa) is given. The structural arrangement of bpa in the solid state was determined by X-ray diffraction. Complexes of Ag(I), Cu(I), Cu(II) and Cd(II) formed with this ligand were synthesised and characterised. The complexes {[Ag(bpa)(MeCN)](CF₃SO₃)}n̲, {[Ag(bpa)](PF₆)�MeCN}n̲, {[Ag(bpa)](ClO₄)-�2MeCN}n̲, {[Ag(bpa)](ClO₄)}n̲, {[Ag(bpa)](NO₃)}n̲, [(Cu₂I₂)(bpa)₂]n̲, {[Cu(bpa)₂Cl₂]-�3DMF�3/2H₂O}n̲, {[Cd(bpa)₂(NO₃)(H₂O)](NO₃)}n̲, {[Cd(bpa)₂(SO₄)(H₂O)]�3H₂O}n̲, [Cd(bpaH)₂(SO₄)₂(H₂O)₂]�2MeCN and {[Cd(bpa)(SCN)₂]�1/5iPrOH}n̲ were structurally characterised by X-ray diffraction. All complexes with Ag(I) were one-dimensional coordination polymers, with two of them helical, the other three zigzag. Both complexes with Cu(I) and (II) were two-dimensional coordination polymers. One complex with CdSO₄ was discrete, with the bpa ligands mono-protonated, but all other three other Cd(II) complexes were three-dimensional coordination polymers. Seven of these complexes showed hydrogen-bonding interactions linking them together to form supramolecular structures of higher dimensionalities. A comparison of the twelve structures is given at the end of the chapter. Chapter five is a brief summary of the outcomes of this thesis.

In dieser Arbeit wurden die Molekülstrukturen und die elektronischen Eigenschaften von Vanadium(IV)- und Oxo-Rhenium(V)-Chelaten mit einem kombinierten molekülmechanisch-quantenchemischen Ansatz untersucht, um sterische und elektronische Effekte der Komplexierung mit einem theoretischen Modell zu quantifizieren. Es konnte gezeigt werden, daß auf diese Weise detaillierte Aussagen zu den Bindungsverhältnissen der Metallchelate getroffen werden können. Die Berechnung der Molekülstrukturen gelingt mit exzellenter Übereinstimmung mit den Kristallstrukturen der Komplexe. Die molekülmechanischen Berechnungen erfolgen auf der Grundlage des Extensible Systematic Force Field ESFF und des Consistent Force Field 91 (CFF91). Dabei konnte die hohe Flexibilität und Zuverlässigkeit des regelbasierten ESFF für eine Vielzahl verschiedenster Metallchelate nachgewiesen werden. Aufgrund der mangelhaften Ergebnisse für trigonal-prismatische Komplexgeometrien mit dem ESFF wurden eine Anpassung des CFF91 für derartige Vanadiumkomplexe vorgenommen. Auf Grundlage von theoretischen Ergebnissen wurden die alternativen Strukturen von isoelektronischen Vanadiumkomplexen berechnet und in Übereinstimmung mit experimentellen Daten, theoretischen Modellen der Komplexchemie und empirischen Fakten eine Hypothese für die Ursache der strukturellen Differenzen erarbeitet.<br> Der hier vorgestellte, kombinierte Algorithmus aus kraftfeldbasierter Geometrieoptimierung und single-point-Rechnung an diesen Strukturen ist ein zuverlässiger und relativ schneller Weg Molekülgeometrien von Metallkomplexen zu berechnen. Er kann somit zur Voraussagen von Komplexstrukturen und zur gezielten Modellierung definierter Koordinationsgeometrien verwendet werden. / In this work the molecular structures and the electronic properties of Vanadium(IV)- and Oxo-Rhenium(V)-chelates have been investigated to quantify steric and electronic effects of complexation. It has been shown, that in this way detailed insight can be gained into the bonding conditions of that metal complexes. Molecular mechanic calculations based on the Extensible Systematic Force Field (ESFF) and the Consistent Force Field 91 (CFF91) have been carried out. High flexibility and reliability of the rule based ESFF has been proven for a large variety of different metal chelates. Due to the poor ESFF-results for trigonal-prismatic complex geometries, a fit of the CFF91 for that species was done. Based on the theoretical results the alternative structure of isoelectronical vanadium(IV)- complexes have been calculated and a hypothesis on the reason for the structural differnces have been stated in accordance with experimental results, theoretical models of complex chemistry, and empirical facts. This combined approach of force field based geometry optimization and single point calculation at these structures has been proven to be a reliable and fast way to get molecular structures of metal complexes. It can be used to predict complex structures for modelling destinct coordination geometries.

N-Heterocyclic carbenes (NHCs) are good ligands to most transition metals forming stable complexes. Many of the NHC-metal complexes are now widely used catalysts. However, the usage of these catalysts encounters the general problems associated with homogeneous catalysis: the purification of the catalysis reaction products is often time-consuming and generates large amounts of waste. Moreover, the toxic or expensive catalysts are difficult to be separated, recycled, and reused. Chapters II and III of this dissertation focus on addressing these problems through the development of an easier and “greener” process to improve the usage of some NHC-metal complexes. Polymer-supported catalysts and polymer-supported sequestrants were prepared and used to facilitate the separation/recycling of catalysts and the purification of products. These polymer-supported ligands, catalysts, and sequestrants showed comparable reactivity to their low molecular weight counterparts and had different solubility properties due to the nature of polymers. Using these materials with the corresponding operations provides simple methods to separate deeply colored, metal-containing by-products from the reaction mixtures. Chapter IV of this dissertation aims at solving a fundamental question about the nature of NHC-silver(I) complexes. The NHC-silver(I) complex is an important synthetic intermediate as it can be used to prepare other NHC-metal complexes through transmetallation. The carbene carbon of an NHC-silver(I) complex in 13C NMR spectra was usually reported as a doublet of doublets or as a singlet in different cases. This phenomenon was explained with a ligand exchange mechanism proposed twelve years ago. However, few reports are available in the literature about the mechanism of the NHC ligand exchange processes at silver. In order to facilitate the study of the solution behaviors of NHC-silver(I) complexes, 13C-labeled NHC-silver(I) complexes were prepared and studied using variable temperature 13C NMR spectroscopy. This study could be useful for future applications of ligand transferring from silver to other metals for the preparation of NHC-metal complexes.

Thesis (Ph. D.)--University of Chicago, Department of Chemistry, 2002. / Includes bibliographical references. Also available on the Internet.

Thesis (Ph.D.)--University of Western Sydney, 2008. / A thesis presented to the University of Western Sydney, College of Health and Science, School of Biomedical and Health Sciences, in fulfilment of the requirements for the degree of Doctor of Philosophy. Includes bibliographies.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy