No description available.

This work aims to define the modes of action of a series of metal extraction ligands with particular focus on how these depend on the formation of supramolecular assemblies. Though solvent extraction processes are well established industrially often the understanding, particularly of the metal coordination chemistry, is less so. A greater understanding of a variety of solvent extraction systems can lead to the development of stronger and more specific extractants. Chapter 2 examines the role of inter-ligand interactions in the extraction of copper by phenolic oximes and pyrazoles. Computational methods are used to understand the importance of inter-ligand outer-sphere interactions in square-planar copper complexes. It is shown that functionalisation at different positions on the phenol ring can either stabilise or destabilise the copper complex and it is possible to predict the strength of extractants from DFT calculations. Substitution ortho to the phenolic oxygen in the oximes and pyrazoles can have a major effect of enhancing the strength of extractants by “buttressing” the H-bonding between ligands. However, in the amino-methyl substituted oximes buttressing is so strong that is has an adverse effect on complex formation. Crystal structures are confirmed by both ENDOR EPR spectroscopy and DFT structures. A series of 6-X-4-methyl-2-(5-alkyl-1H-pyrazol-3-yl)- phenols (X = H, OMe, Br and NO2) was synthesised and characterised (X = H, OMe, Br and NO2) and the copper extractant found to be 6-nitro-4-methyl-2-(5-(1,3,5-tri-methyl-pentyl)- 1H-pyrazol-3-yl)-phenol extractants. Computational DFT studies in the gas phase were carried out to calculate the formation energies of analogous phenolic pyrazole copper complexes. The predicted order of these energies followed the same trend shown by experimental solvent extraction studies. Studies also showed that substitution can affect not only complex stability through inter-ligand interactions through hydrogen bonding in the outer-sphere but also the strength of metal-ligand bonds. Chapter 3 looks at synergistic solvent extraction systems: where more than one extractant works together to provide additional strength and selectivity. Combinations of neutral N and O donor ligands with carboxylic, phosphinic and sulfonic acids were studied by solvent extraction, crystallographic and computational methods. Crystal structures and DFT-optimised structures show that ligands and acid form pseudo-tridentate ligands where both the neutral ligand and the deprotonated acid are coordinated directly to the metal centre with inter-ligand hydrogen bonding allowing for a more flexible backbone than a classic tridentate system. Although synergistic extractions systems often utilise carboxylic acids many of the structures show the similarities with systems containing phosphinic acids and it was shown experimentally that some extraction systems show greater synergism with phosphinic than carboxylic acid in the recovery of nickel. Chapter 4 deals with the extraction of molybdenum with commercial phosphinic acid extractant Cyanex 600. The propensity for molybdenum to form oxo clusters in aqueous solutions and the influence pH in both the speciation of the Mo species and extraction conditions contributes to a complex extraction profile. The pH dependence of extraction shows that different mechanisms operate at low (pH < 0) and high (pH > 0) pH. The extraction curve shows a conventional S-curve between pH 0 and 1.5 and slope analysis within this pH range gives a value very close to two but identification of structures which match this profile is complex. Maximum pH extraction is see at ~ pH 1.5. ESMS studies identified very similar species in the organic phase despite the variation seen in the S-curve. A survey of the structures of metal complexes of phosphinate ligands suggests that molybdenum-phosphinate complexes can often form cubane-like structure and negative ion ESMS data supports the concept of cluster formation in the organic phase. A common feature of the spectra are tetra- tri- and bi-metal- oxo species and spectra show a large number of peaks. It is very probable that the extraction of molybdenum(VI) with phosphinic acids is a dynamic system as extraction is influenced by the molybdenum speciation in the aqueous phase which is in turn influenced by both the pH and the molybdenum concentration both of which change over the course of a conventional extraction.

Based on the concept of covalent capture of supramolecular assemblies, the idea of mechanical encapsulation is exploited for the protection and delivery of peptidebased molecules. This thesis aims to establish a general method for the encapsulation of peptides within a rotaxane structure, as well as studying their mode of release under specific stimuli. The synthesis of such structures, relying on the elongation of short peptido[2]rotaxanes, is applied to the design of rotaxane peptide carriers whose function is to protect against biological degradation and release peptides under a biological stimulus. These molecules are composed of a rotaxane-encapsulated peptide bearing a biodegradable stopper, the enzyme-specific cleavage of which triggers peptide release, via ‘dethreading’. The synthesis and in vitro assessment of rotaxane carriers as agents for anti-cancer therapy will be described in detail. The future challenges and potential applications of the proposed systems will be addressed.

Cette thèse est consacrée au développement d'assemblages supramoléculaires, qui miment la nature amphiphile des membranes cellulaires. A cette fin, des bicouches lipidiques supportées (SLB) ont été conçues pour l'insertion de la FhuA (protéine de membrane externe d’E. coli). L'interaction de FhuA présente dans la SLB, avec le pb5 (la protéine du bactériophage T5) a ensuite été étudiée par QCM-D. De plus, des bicouches lipidiques suspendues (tBLM) ont été construites sur des monocouches auto-assemblées (SAM) d'un nouveau thiol d'ancrage. Dans cette étude, la formation de tBLM a été minutieusement étudiée par différentes techniques telles que la QCM-D, l'AFM et l'EIS, afin de déduire le rôle du thiol d’ancrage dans le processus de formation de tBLM. En outre, un amphipol biotinylé (B-PCApol), a été employé pour l’immobilisation des protéines membranaires, par exemple la FhuA et de l'intégrine avß3 (humain) sur des surfaces contenant la streptavidine. Avec leurs assemblages respectifs, la constante de dissociation du complexe FhuA-pb5 a été déterminée, tandis que les interactions de l'intégrine avec vitronectine (son ligand naturel) ont été étudiées par SPR. La dernière partie de cette thèse est dédiée à l'étude d'événements de reconnaissance biomoléculaire entre une lectine (ConA) et des sucres multivalents présentés sur un châssis moléculaire, RAFT. / This thesis is dedicated towards the development of supramolecular assemblies, which are capable of mimicking the amphiphilic nature of the cytoplasmic cell membranes. To this effect, Supported Lipid Bilayers (SLB) was designed to incorporate FhuA (an E.coli outer membrane protein). The interaction of FhuA present in the SLB, with pb5 (the bacteriophage T5 protein), was then studied using QCM-D. Further, Tethered Lipid Bilayer Membranes (tBLM) were constructed on Self-Assembled Monolayers (SAMs) of a novel synthetic anchoring thiol. In this study, the tBLM formation was elaborately investigated using a host of techniques such as QCM-D, AFM and EIS, to infer upon the role of the anchoring thiol in the tBLM formation process. Further, a biotinylated Amphipol (B-PCApol) was employed to immobilize membrane proteins such as FhuA and the human αvβ3 integrin on streptavidin containing surfaces. Using their respective assemblies, the dissociation constant of the FhuA-pb5 complex was determined, whereas the interactions of integrin with its ligand vitronectin were studied by SPR. The last part of this thesis, deals with the study of biomolecular recognition events between a lectin (ConA) and multivalent sugars presented on a RAFT scaffold.

xvii, 147 p. : ill. (some col.) A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / Supramolecular chemistry is a relatively new and exciting field offering chemists simplistic approaches to generating complex assemblies through strategically designed ligands. Much like the many spectacular examples of supramolecular assemblies in nature, so too are chemists able to construct large, elegant assemblies with carefully designed ligands which bind preferentially to target metal ions of choice. An important concept of supramolecular chemistry, often subtle and overlooked, is secondary bonding interactions (SBIs) which in some cases, act as the glue to hold supramolecular assemblies together. This dissertation examines SBIs in a number of systems involving the pnictogen elements of arsenic and antimony as well as aromatic interactions in self-assembled monolayers. The first half of this dissertation is an introduction to the concepts of supramolecular chemistry and secondary bonding interactions and how they are used in the self-assembly process in the Darren Johnson laboratory. Chapter I describes how secondary bonding interactions between arsenic and aryl ring systems and antimony and aryl ring systems assist with the assembly process. Chapter II is a continuation of the discussion of SBIs but focuses on the interactions between arsenic and heteroatoms. The second half of this dissertation will describe work performed in collaboration with Pacific Northwest National Laboratory (PNNL) in Richland, WA. This work was performed under the guidance of Dr. R. Shane Addleman in conjunction with Professor Darren W. Johnson of the University of Oregon. This portion describes novel systems for use in heavy metal ion remediation from natural and unnatural water sources. Chapters III-V describe functionalized mesoporous silica for use in heavy metal uptake from contaminated water sources. Chapter V describes a new technology invented during this internship at PNNL which utilizes weak bonding interactions between aryl ring systems to produce regenerable green materials for toxic metal binding. This work is ongoing in the Darren Johnson lab. This dissertation includes my previously published and co-authored material. / Committee in charge: Michael Haley, Chairperson, Chemistry; Darren Johnson, Member, Chemistry; Shih-Yuan Liu, Member, Chemistry; James Hutchison, Member, Chemistry; Eric Johnson, Outside Member, Biology

La photocatalyse hétérogène est une technique d'oxydation avancée prometteuse dans le domaine de la dépollution d’effluents aqueux ou gazeux industriels contenant des composés organiques tels que les colorants, engrais, pesticides ou composés organiques volatils (COV). La photocatalyse met en oeuvre l'excitation d’un matériau semi-conducteur par une radiation lumineuse et dans ce contexte le dioxyde de titane (TiO2) est le photocatalyseur le plus couramment employé. Cependant, son activité est liée à de nombreux paramètres (longueur d'onde d'irradiation, paramètres texturaux, composition cristalline…) qu'il convient de maitriser si on veut concevoir un système de dépollution efficace. Afin d’améliorer les performances du TiO2, différentes approches ont émergé durant les dernières décennies, telles que ledopage par des métaux de transition ou le dopage par des composés organiques.Le sujet de la thèse s’est inscrit dans ce contexte et a porté sur le développement de systèmes photocatalytiques élaborés en présence de cyclodextrines (molécules cages formées par l’enchainement d’unités glucosidiques) pour la dégradation de polluants organiques en phase aqueuse. Il s'articule en trois parties principales. La première partie a été consacrée à la possibilité de combiner directement l’action d’un dioxyde de titane commercial (P25) en suspension aqueuse en présence de cyclodextrines pour améliorer le rendement de réactions photocatalysées. Appliquée à la dégradation photocatalytique d’un COV hydrophobe (toluène) dans l’UV, l’étude n’a pas montré d’impact positif des cyclodextrines. Les résultats ont été rationnalisés par l’évaluation des capacités d’adsorption des cyclodextrines sur la surface duphotocatalyseur et des constantes d’association 1:1 CD:toluène. Le deuxième partie a porté sur la synthèse d’une série de matériaux mésoporeux TiO2 par voie sol-gel colloïdale en utilisant comme agents structurants des assemblages supramoléculaires de type Pluronic 123-cyclodextrine partiellement méthylée (micelles). L’introduction de cyclodextrine méthylée en quantité contrôlée permet de jouer sur le glonflement des micelles. Après élimination de l’agent template par calcination, il est mis en évidence qu’il est possible de moduler les paramètres texturaux et structuraux du dioxyde de titane. Ces matériaux ont été évalués dans la réaction de dégradation de l’acide phénoxyacétique en phase aqueuse sous une irradiation proche du rayonnement visible (365 nm). Dans la troisième partie, le développement de matériaux mésoporeux TiO2 par voie sol-gel colloïdale a été poursuivi en substituant les assemblages supramoléculaires comme agents structurants par des cyclodextrines seules. Les paramètres de synthèse ont été optimisés avec différentes types de cyclodextrines (natives ou modifiées) et différentes concentrations.Les meilleurs résultats en termes de dégradation photocatalytique de l’acide phénoxyacétique à 365 nm ont été obtenus avec le matériau R25-T500 préparé à partir de cyclodextrine alétoirement méthylée à 25 g/L. Enfin, l’incorporation d’or sous forme HAuCl4 durant le protocole de synthèse a même permis d’observer une augmentation de l’activité photocatalytique sous irradiation à 420 nm comparativement au catalyseur référence TiO2 P25. / Photocatalysis is a promising advanced oxidation process (AOPs) to efficiently removing non biodegradable pollutants from atmosphere. Among photocatalysts, titanium dioxide (TiO2) remains certainly one of the most attractive materials because it is relatively inexpensive, nontoxic and photochemically stable. However, several factors such as wavelength of irradiation, the crystal phase composition, the surface area and the adsorption properties of the catalyst are likely to affect the hotocatalytic efficiency. The design of semiconductor metal oxide nanoparticles with tunable pore size and morphology andcontrollable composition is so important to create an efficient remediation process. To improve the photoactivity of the semi-conductor, several approaches have already been reported such as the combination of metallic or organic material to titanium dioxide. Cyclodextrins (CDs) are natural cyclic oligosaccharides derived from starch that can include in their hydrophobic cavity many organic compounds by host-guest interaction and thus increase the solubility of the guest. Taking advantage of their inclusion capacity, CDs can play a major role in catalytic processes. Numerous works involving the combined use of cyclodextrins and titanium dioxide have been reported but depending on the structure of the reactants and the reaction conditions, the CD may or may not improve the photocatalytic degradation of pollutants and it seems difficult to predict the effect of CDs on a photocatalytic process. To further understand the interactions between CD and TiO2 and to improve the performance of a photocatalytic remediation process, we studied the effect of different CDs on the properties of commercial or synthesized titanium dioxide nanoparticules. The performances of our catalysts were evaluated on thephotodegradation of two pollutants in aqueous phase: the toluene (VOC) and the phenoxyacetic acid (herbicide). This work has been divided into 3 parts: first we evaluated the impact of different CDs on the photocatalytic degradation of toluene in aqueous phase by a commercial titanium dioxide (P25). Then in a second part we investigated a template-directed colloidal self-assembly strategy for the production, in aqueous phase, of nanostructured TiO2 materials with tunable porosity and crystalline framework. The approach employs the supramolecular assemblies formed between a methylated β-cyclodextrin and the block copolymer P123 as soft templates and TiO2 nanocrystals as building blocks. Finally, we have investigated the possibility of using the cyclodextrin alone as soft templates for the preparation of a series of mesoporous titania materials with tunable properties The results show that a modified cyclodextrin can modulate the textural and structural parameters of TiO2 in order to maximize the degradation of phenoxyacetic acid in aqueous phase under near visible radiation. The incorporation of gold in our synthesis method has even increased the photocatalytic activity of our semi-conductor compared to the commercial P25 for an irradiation of 420 nm.

No description available.

This thesis deals with the investigation of the first hyperpolarizabilities (β) of a large number of molecules linked to other molecules either covalently or noncovalently. Chapter 1 gives a brief introduction to supramolecular chemistry and Nonlinear Optics (NLO). A survey of literature pertinent to noncovalently interacting supramolecular assembly and their NLO properties as well as NLO properties of oligomeric systems has been presented. The scope of the present investigation has been described at the end of the chapter. Chapter 2 discusses all the methods used in carrying out this thesis work. The first hyperpolarizabilities (β) of all the compounds have been measured by the hyper Rayleigh scattering (HRS) technique; the experimental details of which are written in this chapter. Various spectroscopic techniques such as NMR, IR, UV-Vis, etc. that were used in the investigation have been presented. The subsequent chapters 3-5 deal with the actual results obtained in this work. In chapter 3 first hyperpolarizabilities of o-, m-, and p-aminobenzoic acids and their oligomers viz., dimer, trimer and tetramer (covalently linked) have been studied. The compounds are synthesized and characterized by various spectroscopic methods and their β values have been measured by HRS. The hyperpolarizability increases in going from the monomer to the dimer but decreases subsequently from the dimer to the trimer to the tetramer. This unexpected trend in β has been attributed to the formation of molecular aggregates in the trimers and tetramers. Further evidences of aggregation come from the results of1H NMR spectroscopy and conductivity measurements. In chapter 4, synthesis, characterization and HRS investigation to probe the formation, dissociation and binding constants of hydrogen bonded supramolecular complexes (noncovalent interaction) formed in solution between 6-amino-2-(pivaloylamino)pyridine and ferrocene functionalized barbituric acid and 5-methoxy-N,N′-bis(6-amino-2-pyridinyl)-1,3-benzenedicarboxamide and ferrocenyl barbituric acid have been described. From the HRS data the stoichiometry of the supramolecular complexes has been determined and compared to that from the NMR data. Some of the complex stoichiometries that are measured by HRS have not been seen in the NMR data and vice versa. The results have been rationalized in terms of the strengths and weaknesses of various spectroscopic methods as applied to this problem. Many fold increase in the β value has been realized in the supramolecular complex formation process. Depolarized HRS experiments have been carried out to obtain structural information on the complexes. In the last chapter the synthesis, characterization and measurements on the first hyperpolarizabilities of unsubstituted tetraphenylporphyrin and its metallated complexes have been presented. Synthesis of supramolecular complexes of ferrocenyl barbituric acid with functionalized porphyrin compounds has been carried out although the amount of the final complex was insufficient for HRS measurements. This chapter ends with a perspective for the future work in the direction.

Durant longtemps la spectroscopie RMN en solution a été limitée à de petits objets biologiques. Aujourd'hui, il est clairement reconnu que la stratégie du marquage isotopique spécifique de groupements méthyle dans une protéine perdeutérée a considérablement repoussé la frontière de cette technique. En effet, des protéines aussi grande que 1 MDa ont pu être récemment étudiées par RMN. Cependant, cette stratégie présente un inconvénient important lié au nombre réduit de sondes protonées. Dans ce contexte, le projet de thèse vise a développer de nouvelles méthodes pour faire face à cette rareté d'information structurale, en s'appuyant sur le marquage simultané (combinatoire) de plusieurs groupements méthyle afin d'augmenter le nombre de sondes. Pour un marquage combinatoire optimal, le choix des acides aminés à marquer et les précurseurs à utiliser ainsi que le protocole de leur incorporation doit être judicieusement étudié. Dans le présent travail, un nouveau protocole a été mis en place pour un marquage AbId1(LV)proS optimisé, exempt de toutes fuites isotopiques. En comparaison avec le marquage “AbId1LV standard", le modèle proposé permet la diminution d'un facteur de 2 le nombre de signaux RMN des Leu et Val et améliore par un facteur de 4 l'intensité des nOes à long portée qui sont expérimentalement détectable. Par ailleurs, ce protocole permet également la suppression des corrélations parasites, particulièrement nocives pour les études structurales basées sur la détection / analyse de nOes. Afin d'exploiter les spectres RMN obtenus en utilisant le protocole ci-dessus mentionné, l'attribution des signaux des méthyles est obligatoire. Deux stratégies ont été donc proposées. La première s'applique aux systèmes dont le poids moléculaire ne dépasse pas les 100 kDa (e.g. MSG). Elle se repose sur la linéarisation du marquage isotopique des acides aminés permettant ainsi l'utilisation de l'expérience 13C-TOCSY pour attribuer de manière régio et stéréo-spécifique les méthyles de l'isoleucine, leucine et valine en une seule étape. En ce qui concerne la seconde, adaptée aux protéines supra-moléculaire (> 100 kDa), c'est une optimisation de l'approche SeSAM (Sequence-Specific Assignment of Methyl groups by Mutagenesis) précédemment décrite dans la littérature. En effet, grâce au milieu de culture enrichi, mit au point pour le marquage spécifique de l'Ala, le volume minimal de culture requis a été considérablement diminué. Ceci a permis par conséquence de produire les protéines dans des plaques de 24 puits et de les purifier dans des plaques de 96 puits, raccourcissant ainsi le temps global de préparation des échantillons. Il a été estimé que l'utilisation de cette version améliorée de SeSAM offre la possibilité d'attribuer environ 100 méthyles en 2 semaines, dont 4 jours de temps de RMN, en consommant moins de 2 k € de matériaux isotopiques. Pour illustrer la pertinence du marquage isotopique et la protonation sélectifs des méthyles, de façon combinée ou pas, de nombreuses applications ont été présentés, à savoir l'étude en temps réel des processus d'auto-assemblage d'une protéine supramoléculaire (PhTET-2, ~ 0,5 MDa) par RMN. Le marquage combinatoire des protéines (82 kDa et 0,5 MDa) pour la détection de nOes longue portée (jusqu'à 10 Å et 8 Å respectivement) a également été étudié. Cette même approche a également été utilisée pour le filtrage de nOes inter-monomères à long portée, qui sont particulièrement importants pour le calcul de structure, dans des systèmes symétrique et homo-oligomèriques (PhTET-2). / Solution NMR spectroscopy has been limited to small biological objects for a long time. Nowadays, it is unequivocally recognized that the strategy of specific isotope labeling of methyl groups in a perdeuterated protein has significantly extended the frontier of this technique. Indeed, proteins as large as 1 MDa could be investigated by NMR. Conversely, this strategy presents an important drawback consisting of the drastically reduced number of protonated probes. The project of this thesis falls within the framework of developing new methodologies to cope with this scarce structural information, relying on the simultaneous labeling of several methyl groups to increase the number of probes. For optimized combinatorial labeling, the choice of the ensemble of amino acids to label simultaneously and the precursors as well as the protocol for their incorporation have to be carefully studied. In this work, a new protocol was introduced for the scrambling-free and optimized isotopic labeling of AbId1(LV)proS methyl groups. In comparison to the “standard AbId1LV” labeling scheme, the proposed pattern induces a 2-fold decrease of number of Leu and Val NMR signals and enhances the intensity of detectable long-range nOes by a factor 4. The described protocol also permits the suppression of spurious correlations, especially harmful for structural studies based on detection/analysis of nOes. To make an efficient use of the obtained high quality NMR spectra using this protocol, assignment of the methyl groups signals is mandatory. Two strategies were then proposed. The first is suitable for systems whose molecular weight does not exceed 100 kDa. It relies on the use of isotopically linearized precursors (with different isotope topologies to discriminate each methyl group) to assign in a regio- and stereo-specific manner the isoleucine, leucine and valine methyl groups in a single step, employing an optimized “out and back” 13C-TOCSY pulse sequence. While the second, adapted to supra-molecular proteins (> 100 kDa), consists of optimizing the previously reported SeSAM approach (Sequence-Specific Assignment of Methyl groups by Mutagenesis). Indeed, thanks to the developed enriched culture medium for the specific labeling of Ala, the minimal required culture volume was significantly decreased, enabling the proteins expression in 24 well plates and their parallel purification in 96 well plates. This improved SeSAM version was estimated to allow the assignment of ca. 100 methyl cross-peaks in 2 weeks, including 4 days of NMR time and less than 2 k€ of isotopic materials. To illustrate the pertinence of using selectively protonated methyl groups, either in a single or combined fashion, several applications were presented, namely the real-time NMR study of self-assembly process of a ~0.5 MDa supra-molecular protein (PhTET-2). The use of combinatorial labeling for the detection of long-range nOes to up to 10 Å (8 Å) in proteins of 82 kDa (respectively 0.5 MDa) was also investigated. This same approach was exploited for the filtering of inter-monomeric long-range nOes in the same symmetrical and homo-oligomeric PhTET-2 protein.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work presents the synthesis of new compounds and their triazenes complexes of mercury(II). Triazenes have three nitrogen atoms connected in sequence [ N=N N(H) ] and, when deprotonated, they become good Lewis bases and work as excellent ligands in coordination chemistry. Varying the substituent groups bound to the terminal phenyl rings triazenes chain, using substituent groups such as: oxime, fluoro, acetyl, methoxy and nitro. The characterizations were performed with different techniques: x-ray diffraction on single crystal, thermogravimetric analysis (TGA), spectroscopy in the ultraviolet-visible, infrared and hydrogen nuclear magnetic resonance. The main goal this work is the structural characterization by x-ray diffraction of three pre-ligant and ten mercury(II) complexes, with emphasis on supramolecular architectures on solid state. The insertions of the substituent groups favored the formation of supramolecular structures via intermolecular bonds of different type, such as classic and non-classic hydrogen bonds, π stacking interactions, interactions arene C-H∙∙∙π interactions and metal-arene π. The pro-ligands were synthesized are: 1,3-bis(3-phenylacetophenone oxime)triazene; 1-(3-phenyl-acetophenone oxime)-3-(2-fluorophenyl)triazene; 1,3- bis(4-phenyl-acetophenone oxime)triazene; 1-(3-phenyl-acetophenone oxime)-3-(2-methoxy-4- nitrophenyl)triazene; 1-(4-phenyl-acetophenone oxime)-3-(2-methoxy-4-nitrophenyl)triazene; 1,3- bis(4-acetylphenyl)triazene; 1-(3-phenyl-acetophenone oxime)-3-(4-nitrophenyl)triazene; 1-(4- acetilphenyl)-3-(4-nitrophenyl)triazene. Were synthesized ten new complexes of mercury(II) by varying the ligands and the stoichiometry of the reactions. The complexes were synthesized are: bis[1,3-bis(4-phenylacetophenone oxime)triazenide]mercúrio(II); bis[1,3-bis(3-phenylacetophenone oxime)triazenide]mercúrio(II); bis[3-(4-phenylacetophenone oxime)-1-(4-nitrophenyl)- triazenide]mercúrio(II); {[1,3-bis(4-phenylacetophenone oxime)triazenide](acetate)mercúrio(II)}; {[1- (3-phenylacetophenone oxime)-3-(2-metoxi-4-nitrophenyl)triazenide](acetate)mercúrio(II)}; {[1-(3- phenylacetophenone oxime)-3-(2-fluorophenyl)triazenide](acetate)mercúrio(II)}; {[1-(3- phenylacetophenone oxime)-1-(2-metoxi-4-nitrophenyl)triazenide](acetate)mercúrio(II)}; bis{[1,3- bis(4-acetilphenyl)triazenide](triphenylfosfine)mercúrio(II)}; bis{[1-(4-acetilphenyl)-3-(4- nitrophenyl)triazenides](triphenylfosfine)mercúrio(II)}; bis{[1,3-bis(2-methoxy-4- nitrophenyl)triazenide](piridine)mercúrio(II)}. / Este trabalho apresenta a síntese de novos compostos triazenos e seus complexos de mercúrio(II). Compostos triazenos possuem três átomos de nitrogênio ligados em sequencia [ N=N N(H) ] e, quando desprotonados, tornam-se bases de Lewis e atuam como ótimos ligantes na química de coordenação. Variou-se os grupos substituintes nos anéis fenila terminais ligados à cadeia de triazeno, utilizando-se grupos substituintes como: oxima, fluoro, acetil, metóxi e nitro. As caracterizações foram realizadas com diferentes técnicas: difração de raios-x em monocristal, análise termogravimétrica (TGA), espectroscopia na região do ultravioleta e visível, infravermelho e ressonância magnética nuclear de hidrogênio. O objetivo principal deste trabalho foi a caracterização estrutural de três pré-ligantes e dez complexos de mercúrio(II) pela difração de raios-x, com ênfase na supramolecularidade destes compostos. As inserções dos grupos substituintes nos anéis fenila favoreceram a formação de estruturas supramoleculares através de ligações intermoleculares de diferentes tipo, tais como ligações de hidrogênio clássicas e não-clássicas, interações de empilhamento π, interações C−H areno π e interações metal areno π. Os pré-ligantes sintetizados foram: 1,3-bis(3-fenil-acetofenona oxima)triazeno; 1-(3-fenilacetofenona oxima)-3-(2-fluorofenil)triazeno; 1,3-bis(4-fenil-acetofenona oxima)triazeno; 1-(3-fenilacetofenona oxima)-3-(2-metóxi-4-nitrofenil)triazeno; 1-(4-fenil-acetofenona oxima)-3-(2-metóxi-4- nitrofenil)triazeno; 1,3-bis(4-acetilfenil)triazeno; 1-(3-fenil-acetofenona oxima)-3-(4- nitrofenil)triazeno; 1-(4-acetilfenil)-3-(4-nitrofenil)triazeno. Sintetizou-se dez complexos de mercúrio(II), variando-se os pré-ligantes e a estequiometria das reações. Os complexos sintetizados foram: bis[1,3-bis(4-fenilacetofenona oxima)triazenido]mercúrio(II); bis[1,3-bis(3-fenilacetofenona oxima)triazenido]mercúrio(II); bis[3-(4-fenilacetofenona oxima)-1-(4-nitrofenil)- triazenido]mercúrio(II); {[1,3-bis(4-fenilacetofenona oxima)triazenido](acetato)mercúrio(II)}; {[1-(3- fenilacetofenona oxima)-3-(2-metoxi-4-nitrofenil)triazenido](acetato)mercúrio(II)}; {[1-(3- fenilacetofenona oxima)-3-(2-fluorofenil)triazenido](acetato)mercúrio(II)}; {[1-(3-fenilacetofenona oxima)-1-(2-metoxi-4-nitrofenil)triazenido](acetato)mercúrio(II)}; bis{[1,3-bis(4- acetilfenil)triazenido](trifenilfosfina)mercúrio(II)}; bis{[1-(4-acetilfenil)-3-(4- nitrofenil)triazenidos](trifenilfosfina)mercúrio(II)}; bis{[1,3-bis(2-metóxi-4- nitrofenil)triazenido](piridina)mercúrio(II)}.