This thesis contains investigations in the area of polymers herein propellants binders are modified functionally to meet the requirements of future energetic propellants. Chapter 1 contains a broad introduction to the area of recent advances in solid propellants and the numerous applications of ‘Click Chemistry’. Chapters 2 details the materials, characterization tools and the experimental techniques employed for the studies. This is followed by Chapter 3, 4, and 5 which deals with functional modification of various propellants binders, their characterisation and evaluation in propellant formulations. Chapter 6 details with the thermal decomposition of diazides and its reaction with alkenes. The advent of modern rockets has opened a new era in the history of space exploration as well as defence applications. The driving force of the rocket emanates from the propellant – either solid or liquid. Composite solid propellants find an indispensable place, in today’s rockets and launch vehicles because of the inherent advantages such as high reliability, easy manufacturing, high thrust etc. The composite propellant consisting of inorganic oxidiser like ammonium perchlorate, (AP), ammonium nitrate (AN) etc), metallic fuel (aluminium powder, boron etc) and polymeric fuel binder (hydroxyl terminated polybutadiene-HTPB, polybutadiene-acrylic acid-acrylonitrile PBAN, glycidyl azide polymer (GAP), polyteramethylene oxide (PTMO) etc. is used in igniters, boosters, upper stage motors and special purpose motors in large launch vehicles. Large composite solid propellant grains or rocket motors in particular, demand adequate mechanical properties to enable them to withstand the stresses imposed during operation, handling, transportation and motor firing. They should also have a reasonably long ‘potlife’ to provide sufficient window for processing operations such as mixing and casting which makes the selection of binder with appropriate cure chemistry more challenging. In all composite solid propellants currently in use, polymers perform the role of a binder for the oxidiser, metallic fuel and other additives. It performs the dual role of imparting dimensional stability to the composite, provides structural integrity and good mechanical properties to the propellant besides acting as a fuel to impart the required energetics. Conventionally, the terminal hydroxyl groups in the binders like GAP, PTMO and HTPB are reacted with diisocyanates to form a polyurethane network, to impart the necessary mechanical properties to the propellant. A wide range of diisocyantes such as tolylene diisocyanate (TDI) and isophorone diisocyanate (IPDI) are used for curing of these binders. However, the incompatability of isocyanates with energetic oxidisers like ammonium dinitramide (ADN), hydrazinium nitroformate (HNF), short ‘potlife’ of the propellant slurry and undesirable side reactions with moisture are limiting factors which adversely affect the mechanical properties of curing binders through this route. The objective of the present study is to evolve an alternate approach of curing these binders is to make use of the 1,3 dipolar addition reactions between azide and alkyne groups which is a part of ‘Click chemistry’. This can be accomplished by the reaction of azide groups of GAP with triple bonds of alkynes and reactions of functionally modified HTPB/PTMO (azide/alkyne) to yield 1,2,3 -triazole based products. This offers an alternate route for processing of solid propellants wherein, the cured resins that have improved mechanical properties, better thermal stability and improved ballistic properties in view of the higher heat of decomposition resulting from the decomposition of the triazole groups. GAP is an azide containing energetic polymer. The azide groups can undergo reaction with alkynes to yield triazoles. In, Chapter 3 the synthesis and characterisation of various alkynyl compounds including bis propargyl succinate (BPS), bis propargyl adipate (BPA), bis propargyl sebacate (BPSc.) and bis propargyl oxy bisphenol A (BPB) for curing of GAP to yield triazoles networks are studied. The mechanism of the curing reaction of GAP with these alkynyl compounds was elucidated using a model compound viz. 2-azidoethoxyethane (AEE). The reaction mechanism has been analysed using Density Functional Theory (DFT) method. DFT based theoretical calculations implied marginal preference for 1, 5 addition over the 1, 4 addition for the uncatalysed cycloaddition reaction between azide and alkyne group. The detailed characterisation of these systems with respect to the cure kinetics, mechanical properties, dynamic mechanical behaviour and thermal decomposition characteristics were done and correlated to the structure of the network. The glass transition temperature (Tg), tensile strength and modulus of the system increased with crosslink density which in turn is, controlled by the azide to alkyne molar stoichiometry. Thermogravimetic analysis (TGA) showed better thermal stability for the GAP-triazole compared to GAP based urethanes. Though there have been a few reports on curing of GAP with alkynes, it is for the first time that a detailed characterisation of this system with respect to the cure kinetics, mechanical, dynamic mechanical, thermal decomposition mechanism of the polymer is being reported. To extent the concept of curing binders through 1,3 dipolar addition reaction, the binder HTPB as chemically transformed to propargyloxy carbonyl amine terminated polybutadiene (PrTPB) with azidoethoxy carbonyl amine terminated polybutadiene (AzTPB) and propargyloxy polybutadiene (PTPB). Similarly, PTMO was convnerted to propargyloxy polytetramethylene oxide (PTMP). Triazole-triazoline networks were derived by the reaction of the binders with alkyne/azide containing curing agents. The cure characteristics of these polymers (PrTPB with AzTPB, PTPB with GAP and PTMP with GAP) were studied by DSC. The detailed characterisations of the cured polymers for were done with respect to the, mechanical, dynamic mechanical behaviour and thermal decomposition characteristics were done. Propellant level studies were done using the triazoles derived from GAP, PrTPB-AzTPB, PTPB and PTMP as binder, in combination with ammonium perchlorate as oxidiser. The propellants were characterised with respect to rheological, mechanical, safety, as well as ballistic properties. From the studies, propellant formulations with improved energetics, safety characteristics, processability and mechanical properties as well defect free propellants could be developed using novel triazole crosslinked based binders. Chapter 6, is aimed at understanding the mechanism of thermal decomposition of diazido compounds in the first section. For this, synthesis and characterisation of a diazido ester 1,6 –bis (azidoacetoyloxy) hexane (HDBAA) was done. There have been no reports on the thermal decomposition mechanism of diazido compounds, where one azide group may influence the decomposition of the other. The thermal decomposition mechanism of the diazido ester were theoretically predicted by DFT method and corroborated by pyrolysis-GC-MS studies. In the second section of this chapter, the cure reaction of the diazido ester with the double bonds of HTPB has been investigated. The chapter 6B reports the mechanism of Cu (I) catalysed azide-alkene reaction validated using density functional theory (DFT) calculations in isomers of hexene (cis-3-hexene, trans-3-hexene and 2-methy pentene: model compound of HTPB) using HDBAA. This the first report on an isocyanate free curing of HTPB using an azide. Chapter 7 of the thesis summarizes the work carried out, the highlights and important findings of this work. The scope for future work such as development of high performance eco-friendly propellants based on triazoles in conjunction with chlorine-free oxidizer like ADN, synthesis of compatible plasticisers and suitable crosslinkers have been described. This work has given rise to one patent, three international publications and four papers in international conferences in the domain.

Au cours des dernières années, le développement des cellules organiques à réseaux interpénétrés a permis d’améliorer les rendements de conversion photovoltaïque (PV). Ces dispositifs incorporent une couche active constituée d’un mélange d’un matériau donneur d’électron (D) et d’un matériau accepteur d’électron (A). La réalisation de ces cellules requiert une optimisation minutieuse de ce mélange et de la morphologie de cette couche photo-active qui en résulte. Cette dernière peut cependant évoluer spontanément vers une ségrégation de phase, généralement délétère pour les performances PV. Une solution possible, et relativement peu étudiée, consiste à lier chimiquement le donneur D et l’accepteur A par un espaceur non-conjugué. Les travaux décrits dans ce manuscrit portent sur la synthèse et la caractérisation d’assemblages moléculaires de type D-σ-A ainsi que leur utilisation comme matériau dit « unique » pour la fabrication de cellules solaires organiques mono composant. Une première famille de dyades et triades à base d’un bloc donneur de type quaterthiophène a été étudiée. Cette partie décrit la méthodologie générale d’assemblage des blocs D et A via une réaction de cycloaddition de type Huisgen. Au cours des chapitres suivant, plusieurs dyades basées sur un bloc donneur « push-pull » ont été synthétisées puis caractérisées. Les performances PV de ces composés ont été évaluées au sein de cellules solaires mono-composant et les meilleurs rendements de conversion, atteignant 1.4 %, rivalisent avec l’état de l’art. / Over the last few years, the development of bulk heterojunction organic solar cells (BHJ OSCs) led to significant increase in photovoltaic (PV) efficiency. Such devices are based on interpenetrated networks of an electron-donor material (D) and an electron-acceptor material (A) constituting the active layer. Nevertheless a careful optimization of the morphology is required to reach high power conversion efficiency. Furthermore, this optimized morphology can evolve towards spontaneous phase segregation which can be detrimental for the PV performances. To circumvent these limitations, a relatively unexplored approach relies on the use of a material where the donor and the acceptor moieties are covalently linked to each other through a nonconjugated π-connector. In this context, the work reported herein describes the synthesis and characterization of various molecular D-σ-A assemblies, as well as their preliminary evaluation as “unique” material for the realisation of single component organic solar cells (SC-OSCs). A first family of dyads and triads, based on quaterthiophene moieties as donor block, was studied. A general methodology to assemble the two D and A blocks via a Huisgen-type click-chemistry is described. Then, in the next chapters, several dyads based on a “push-pull” donor block have been synthesized and characterized. The PV performances of these compounds have been evaluated in SC-OSCs leading to power conversion efficiency up to 1.4 %, a value close to the state of the art.

Des résultats récents ont montré les premières preuves d’un effet multivalent puissant des iminosucres sur l’inhibition des glycosidases, avec des gains d’affinité allant jusqu’à 10000. Afin de comprendre les différentes caractéristiques de cet « effet de cluster » et d’en poursuivre l’optimisation, de nouvelles charpentes doivent être conçues. Le premier axe de recherche a donc consisté en la mise au point d’un ensemble de techniques d’ingénierie « click » pour la synthèse de systèmes multivalents, avec le développement d’une stratégie Sweet LEGO®. Cette approche permettrait un accès simple à une grande variété de néocyclodextrines préfonctionnalisées. Le second axe a consisté en une étude de relation structure-activité autour de charpentes moléculaires polyalcynes utilisées pour préparer de nouveaux clusters par chimie « click ». Une partie des clusters a été préparée en utilisant de nouvelles charpentes cyclopeptoïdes. Ils ont permis de poursuivre l’optimisation de l’effet multivalent des iminosucres sur l’inhibition de glycosidases. En particulier, un composé portant 30 ligands a montré le meilleur effet multivalent connu sur une enzyme modèle. / Recent reports have demonstrated the first pieces of evidence of a strong multivalent effect in glycosidase inhibition by iminosugars, with affinity enhancements close to 10000. In order to understand the different parameters of this “cluster effect” and to continue its optimization, new scaffolds must be designed. The first research topic was thus to develop a set of « Click » Chemistry engineering techniques for the synthesis of multivalent systems, with the development of a Sweet LEGO® strategy. In the end, it would allow an easy access to a broad range of prefunctionalized neocyclodextrins. The second research topic consisted in a structure-activity relationship study by varying the molecular polyalkyne scaffold used for the preparation of new clusters by way of « Click » Chemistry. They allowed to investigate the specific features of the iminosugar cluster effect in the inhibition of glycosidases. In particular, a compound of unprecedented valency bearing 30 iminosugar units demonstrated an unprecedented dramatic affinity enhancement for the inhibition of a model enzyme (Jack bean alpha-mannosidase).

Dans cette thèse, nous avons développé l'utilisation de l'activation microondes pour fonctionnaliser des pérovskites lamellaires et notamment la phase d'Aurivillius Bi2SrTa2O9 (BST), connue pour ses propriétés ferroélectriques. Nous sommes parvenus à protoner cette phase (HST) et à la fonctionnaliser par diverses amines et polyamines, avec des temps de réaction considérablement réduits par rapport aux fonctionnalisations en conditions classiques. Cette approche nous a permis de fonctionnaliser HST par des amines plus encombrées et plus complexes. Cette stratégie a ensuite été étendue au greffage d'alcools et de polyols. Nous avons également établi une stratégie de modification post-synthèse, pour synthétiser in situ la molécule désirée, en utilisant la chimie "click" et l'activation microondes. Enfin, nous sommes parvenus à insérer des ions métalliques et des complexes de métaux de transition, ce qui constitue une première étape vers la synthèse de nouveaux hybrides multiferroïques. / During this PhD thesis, we have developed the use of microwave activation to functionalize layered perovskites, among which the Aurivillius phase Bi2SrTa2O9 (BST), known for its ferroelectric properties. We managed to protonate this phase (leading to HST) and to functionalize it by various amines and polyamines, with reaction times much shorter than using classical conditions. This approach allowed us to functionalize HST by bulkier and more complex amines. This strategy has further been extended to the grafting of alcohols and polyols. We have also established a postsynthesis modification strategy, in order to synthesize the desired molecule in situ, within the interlamellar space, using "click" chemistry and microwave activation. Finally, we managed to insert transition metal ions and complexes, which constitutes a promising step towards the synthesis of new multiferroic hybrid materials.

Les travaux présentés dans cette thèse s’inscrivent dans une thématique de modification de surfaces par le biais de monocouches auto-assemblées post-fonctionnalisables. L’objectif principal consiste à élaborer une méthode générique de modification de monocouches par des motifs moléculaires variés. Pour cela, les travaux se concentrent sur la mise au point d’une plateforme générique facilement fonctionnalisable par un motif d’intérêt et greffable sur électrode modifiée. La voie retenue consiste à utiliser deux réactions de "click chemistry" de type "CuAAC". La première réaction de CuAAC s’effectue en solution et permet de solidariser plateforme et motifs d’intérêt (principalement des dérivés ferrocényles). Les ligands ainsi obtenus ont été utilisés pour la complexation d’ions métalliques (Cu2+, Zn2+). Les ligands et les complexes ont été étudiés en solution par électrochimie ainsi que par spectroscopies UV-Visibles et RPE. La seconde réaction de CuAAC permet l’immobilisation des différents complexes de cuivre sur des électrodes pré-modifiées par des fonctions azoture, généralement à l’aide de monocouches auto-assemblées. Ce greffage s’effectue selon le mode opératoire de l’"électroclick auto-induite", c'est-à-dire que le complexe de cuivre à immobiliser est également catalyseur de la réaction de CuAAC. Les systèmes ainsi immobilisés (mono-, bi- ou tri-métalliques) ont pu être étudiés en terme de cinétique d’immobilisation, de cinétique de transfert d’électrons et en réactivité. Ce dernier point a par ailleurs fait l’objet d’une attention particulière pour le cas de la réduction électro-catalytique des ions nitrite par les complexes de cuivre (I), en solution et sur surface. / This work depends on functionalized surface theme using modification of selfassembled monolayers (SAMs). The main objective consists to elaborate a new general pathway to modify monolayers with miscellaneous objects of interest. For this, we decide to focus our work to synthesize a versatile platform handling two ethynyl arms. These functions are available to operate two CuAAC reactions. The first one is use for linking platform with object of interest (in general ferrocenyl derivatives). Ligands obtained by that way were used for complexation of Cu2+ and Zn2+ ions. Electrochemical and spectroscopic (UV-Visible and EPR) studies were performed on these compounds. The second CuAAC reaction is used to immobilize copper complexes on azide modified electrode (azide derivatives SAMs on gold and ITO or direct functionnalization of glassy carbon surface). The grafting is operating through “self-induced electroclick” method; this means the CuAAC reaction is catalysed by the copper complex which is immobilized. Functionalized electrodes were characterized by cyclic voltammetry. It appears that similar complexes have closed grafting kinetic. These studies also demonstrate the both influence of copper and spacer on a second electroactive site (ferrocene moieties). The reactivity of copper centre is evaluated for complexes in solution and immobilized on surface with electrocatalytic reduction of nitrite ions by copper (I) species. The catalytic efficiency strongly depends on potential of copper reduction. Also, similar complexes show a loss of catalytic power with immobilization on surface.

A natural phenomenon characterized by dense aggregations of unicellular photosynthetic marine organisms has been termed colloquially as red tides because of the vivid discoloration of the water. The dinoflagellate Karenia brevis is the cause of the Florida red tide bloom. K. brevis produces the brevetoxins, a potent suite of neurotoxins responsible for substantial amounts of marine mammal and fish mortalities. When consumed by humans, the toxin causes Neurotoxic Shellfish Poisoning (NSP). The native function of brevetoxin within the organism has remained mysterious since its discovery. There is a need to identify factors which contribute to and regulate toxin production within K. brevis. These toxins are produced and retained within the cell implicating a significant cellular role for their presence. Localization of brevetoxin and identification of a native receptor may provide insight into its native role as well as other polyether ladder type toxins such as the ciguatoxins, maitotoxins, and yessotoxins. In higher organisms these polyether ladder molecules bind to transmembrane proteins with high affinity. We anticipated the native brevetoxin receptor would also be a transmembrane protein. Photoaffinity labeling has become increasingly popular for identifying ligand receptors. By attaching ligands to these photophors, one is able to activate the molecule after the ligand binds to its receptor to obtain a permanent linkage between the two. Subsequent purification provides the protein with the ligand directly attached. A molecule that is capable of fluorescence is a fluorophore, which upon excitation is capable of re-emitting light. Fluorescent labeling uses fluorophores by attaching them covalently to biologically active compounds. The synthesis of a brevetoxin photoaffinity probe and its application in identifying a native brevetoxin receptor will be described. The preparation of a fluorescent derivative of brevetoxin will be described and its use in localizing the toxin to an organelle within K. brevis. In addition, the general utility of a synthesized photoaffinity label with other toxins having similar functionality will be described. An alternative synthetic approach to a general photoaffinity label will also be discussed whose goal was to accelerate the preparation and improve the overall synthetic yields of a multifunctional label.

Fluorinated nucleosides, especially the analogues with fluorine atom(s) in the ribose ring, have been known to exert potent biological activities. The first part of this dissertation was aimed at developing oxidative desulfurization-fluorination and reductive desulfonylation-fluorination methodologies toward the synthesis of 2'-mono and/or 2',2'-difluoro pyrimidine nucleosides from the corresponding 2'-arylthiopyrimidine precursors. Novel oxidative desulfurization-difluorination methodology was developed for the synthesis of α,α-difluorinted esters from the corresponding α-arylthio esters, wherein the arylthio group is present on a secondary internal carbon. For the reductive desulfonylation studies, cyclic voltammetry was utilized to measure the reduction potentials at which the sulfone moiety of substrates can be cleaved. The 5-bromo pyrimidine nucleosides and 8-bromo purine nucleosides act as crucial intermediates in various synthetic transformations. The second part of the present dissertation was designed to develop a novel bromination methodology using 1,3-dibromo-5,5-dimethylhydantoin (DBH). Various protected and deprotected pyrimidine and purine nucleosides were converted to their respective C5 and C8 brominated counterparts using DBH. The effect of Lewis acids, solvents, and temperature on the efficiency of bromination was studied. Also, N-bromosuccinimide (NBS) or DBH offered a convenient access to 8-bromotoyocamycin and 8-bromosangivamycin. Third part of this research work focuses on the design and synthesis of 6-N-benzylated derivatives of 7-deazapurine nucleoside antibiotics, such as tubercidin, sangivamycin and toyocamycin. Target molecules were synthesized by two methods. First method involves treatment of 7-deazapurine substrates with benzylbromide followed by dimethylamine-promoted Dimroth rearrangement. The second method employs fluoro-diazotization followed by SNAr displacement of the 6-fluoro group by a benzylamine. The 6-N-benzylated 7-deazapurine nucleosides showed type-specific inhibition of cancer cell proliferation at micromolar concentrations and weak inhibition of human equilibrative nucleoside transport protein (hENT1). In the fourth part of this dissertation, syntheses of C7 or C8 modified 7-deazapurine nucleosides, which might exhibit fluorescent properties, were undertaken. 8-Azidotoyocamycin was synthesized by treatment of 8-bromotoyocamycin with sodium azide. Strain promoted click chemistry of 8-azidotoyocamycin with cyclooctynes gave the corresponding 8-triazolyl derivatives. Alternatively, 7-benzotriazolyl tubercidin was synthesized by iodine catalyzed CH arylation of tubercidin with benzotriazole.

Chemical biology encompasses the study and manipulation of biological system using chemistry, often by virtue of small molecules or unnatural amino acids. Much insight has been gained into the mechanisms of biological processes with regards to protein structure and function, metabolic processes and changes between healthy and diseased states. As an ever expanding field, developing new tools to interact with and impact biological systems is an extremely valuable goal. Herein, work is described towards the synthesis of a small library of heterocyclic-containing small molecules and the mechanistic details regarding the interesting and unexpected chemical compounds that arose; an alternative set of non-toxic copper catalyzed azide-alkyne click conditions for in vivo metabolic labelling; and the synthesis of an unnatural amino acid for further chemical modification via [3+2] cycloadditions with nitrones upon incorporation into a peptide of interest. Altogether, these projects strive to supplement pre-existing methodology for the synthesis of small molecule libraries and tools for metabolic labelling, and thus provide further small molecules for understanding biological systems.

Click chemistry is a molecular synthesis strategy based on reliable, highly selective reactions with thermodynamic driving forces typically in excess of 20 kcal mol-1. The 1,3-dipolar cycloaddition of azides and alkynes developed by Rolf Huisgen saw dramatic rate acceleration using Cu(I) as a catalyst in 2002 reports by Barry Sharpless and Morten Meldal enabling its click chemistry eligibility. Since these seminal reports, the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) has become the quintessential click reaction finding diverse utility. The popularity of the CuAAC has naturally led to interest in new catalyst systems with improved efficiency, robustness, and reusability with particular focus on nanomaterial catalysts, a common trend across the field of catalysis. The high surface area of nanomaterials lends to their efficacy as colloidal and heterogeneous nanocatalysts, but the latter boasts the added benefit of easy separation and recyclability. With any heterogeneous catalyst, a common question arises as to whether the active catalyst species is truly heterogeneous or rather homogeneous through metal ion leaching. Differentiating these processes is critical, as the latter would result in reduced efficiency, higher cost, and inevitable environmental and heath side effects. This thesis explores the CuAAC from an interdisciplary approach. First as a synthetic tool, applying CuAAC-formed triazoles as functional, modular building blocks in the synthesis of optical cation sensors by combining azide and alkyne modified components to create a series of sensors selective for different metal cations. Next, single-molecule spectroscopy techniques are employed to observe the CuNP-catalyzed CuAAC in real time. Combining bench-top techniques with single-molecule microscopy to monitor single-catalytically generated products proves to be an effective method to establish catalysis occurs directly at the surface of copper nanoparticles, ruling out catalysis by ions leached into solution. This methodology is extended to mapping the catalytic activity of a commercial heterogeneous catalyst by applying super-localization analysis of single-catalytic events. The approach detailed herein is a general one that can be applied to any catalytic system through the development of appropriate probes. This thesis demonstrates single-molecule microscopy as an accessible, effective, and unparalleled tool for exploring the catalytic activity of nanomaterials by monitoring single-catalytic events as they occur.

Les carbènes N-hétérocycliques (NHC) sont utilisés comme ligands pour les métaux de transition. Les complexes résultants présentent principalement des applications en catalyse, ainsi que dans la conception de nouveaux candidats médicaments. Dans ce travail, nous discuterons une simplification des méthodes de synthèse des sels d’imidazoliniums, ainsi que des complexes Cu- et Ag-NHC. L’ammoniaque est utilisé ici à la fois comme milieu solubilisant des espèces métalliques et comme base pour la déprotonation des sels d’imidazoli(ni)ums fournissant une métallation douce, rapide et simple. La fonctionnalisation des NHC, dans des positions définies, permet une modulation de certaines de leurs caractéristiques sans impacter les propriétés remarquables de leurs complexes. De nouvelles méthodes de fonctionnalisation, par cycloaddition azoture-alcyne en périphérie des noyaux aromatiques, ont été mises au point. Ceci mène à l’introduction de trois stratégies synthétique : pré-, post- et auto-fonctionnalisation. La stratégie de pré-fonctionnalisation de précurseurs permet l’accès à des métallo-NHC du groupe 11, dont les propriétés de solubilité peuvent être facilement modifiées. Des réactions thermiques d’Huisgen et de SPAAC sont réalisables directement sur les complexes Au-NHC modifiés par des azotures, et sont désignés comme post-fonctionnalisation. Des réactions dites d’auto-fonctionnalisations entre un complexe Cu-NHC possédant un azoture et des alcynes divers, permettent l’introduction, par exemple, de biomolécules sensibles sans étapes de protection/déprotection. Enfin, les complexes Cu-NHC fonctionnalisés avec des groupements hydrosolubilisants ont été étudiés en tant que catalyseurs de cycloaddition de CuAAC dans des milieux biocompatibles, tandis que les Ag-NHC fonctionnalisés avec des groupements lipophiles présentent une activité antibactérienne. / N-heterocyclic carbenes (NHCs) have been used very frequently as ligands for the preparation of transition metal-based catalysts as well as drug candidates. This work will present a simplification of imidazoliniums synthesis and a new preparation of Ag-, Cu-NHC complexes. Aqueous ammonia will be used for the solubilisation of metallic species and as a base for the deprotonation of imidazoli(ni)um salts providing a mild, quick and easy metallation procedure. The functionalisation of NHC ligands, in definite positions, allows the modulation of some of their characteristics without interfering with the remarkable properties of their complexes. New functionalisation strategies by azide-alkyne cycloaddition reaction at the periphery of aromatics cores, were developped. This can be described by the following three synthetics strategies: pre-, post- and auto-functionalisation. Pre-functionnalisations strategy of precursors allows the synthesis of coinage metal-NHC complexes, for which variation of solubility is easily obtained. Thermal Huisgen reactions and SPAAC are achievable on the Au-NHC azide modified complexes directly, in a post-functionalisation pathway. Furthermore, the post-functionnalisation strategy was extended to Cu-NHC complexes resulting in an auto-functionalisation process. This allowed subsequently the introduction of sensitive biomolecules without protection/deprotection steps. Finally, water soluble Cu-NHCs complexes were used as CuAAC catalyst in bio-compatible media. Lipophilic Ag-NHCs complexes were tested as antibacterials (antibiofilm and growth inhibition activities).