Organic conjugated polymers (CPs) are emerging materials for advanced electronic applications such as organic photovoltaics (OPVs), field-effect transistors (OFETs), light-emitting diodes (OLEDs), flexible and wearable electronics, and biomedicals. High-spin donor-acceptor CPs have been investigated for their potential applications in magnetic and spintronic devices. Inter-chain charge transfer among these high-spin polymers mainly depends on the nature of the local structure of the thin film and pi-stacking between the polymer chains. However, the microscopic structural details of high-spin polymeric materials are rarely studied, especially in the liquid phase, and remain largely unexplored. This study examined the effects of oligomer chain length, side chain, and processing temperature on the organization of the high-spin cyclopentadithiophene-benzobisthiadiazole donor-acceptor conjugated polymer in chloroform solvent. We have found that the oligomers exhibit ordered aggregation based on chain length, with an average pi-stacking distance of 3.38±0.03 (angstrom), aligning well with the experiment. During the solution processing of CPs, smart polymers are widely used for controlling the device performance. Polymethyl-methacrylate (PMMA) is a smart polymer exhibiting solvation behavior in aqueous alcohol mixtures that is different from individual solvents. However, a thorough understanding of the microscopic details underlying PMMA cosolvency remains elusive, which is essential for tailoring smart polymers for advanced applications. Using molecular dynamics simulation, this study elucidates the PMMA's cosolvency behavior in a binary mixture of aqueous tert-butanol and successfully captures the re-collapsing behavior observed experimentally. We have observed that the excess hydrogen bonding between PMMA and water mimics the re-collapsing pattern, suggesting a key role in PMMA's cosolvency. Efforts to discover new organic molecules are hindered by the vast chemical space. Machine learning (ML) approaches offer a promising solution to accelerate the development of new materials. However, predicting properties accurately with ML models typically involves high computational costs and complexity. This study employs a first-generation ML model, ridge regression, to predict the electronic properties — electronic gap, HOMO, LUMO, and singlet-triplet gap of pi-conjugated organic molecules. This research provides molecular-level insights to control device performance by managing aggregation in thin films and reduces the effort required to screen for desirable organic CPs. These findings will facilitate the development of new organic molecules tailored for advanced electronic devices.

A comparison of the composition and structure of carbon films deposited by ns and fs laser ablation of graphite is the subject of this thesis. In addition, the effect of irradiation on the surface of graphite has been investigated in detail. Laser-induced phase transitions from graphite to sp-bonded carbon and trans-polyacetylene chains as well as the formation of nano-diamond have been observed after irradiation with fs pulses. An optical orientation mechanism involving both electric and magnetic interactions is proposed to understand the formation of nano-stripes and other structures on irradiated graphite surfaces. These phenomena are not observed after nanosecond laser irradiation. Tetrahedral carbon (ta-C) films deposited at cryogenic temperatures using ns laser radiation consist of sub-micron graphitized grains embedded in a matrix of sp3-hybridized bonded carbon. Nano-buckling is evident in ta-C films deposited by fs ablation where the composition is found to consist of mixed sp, sp2, and sp3 – hybridized carbons species. It is found that the concentration of sp-bonded chains is negligible in ns-C films. Surface enhanced Raman spectroscopy has been used to characterize molecular species in ns and fs carbon films. Time of flight mass spectroscopy has been used to study plume species produced by laser ablation. It is also found that polyyne molecules can be formed by fs laser dissociation of small molecules in organic solvents. This process is accompanied by the deposition of hexagonal nano-diamond films on substrates placed near the laser focus during irradiation. This opens a new path in the synthesis of 1D conducting molecules and nano-diamond materials for nano-science applications. Quantum chemical calculations involving density functional theory (Gaussian '03) have been carried out in support of this work and have been used to study Raman and IR vibrational modes of several novel carbon molecules synthesized in ta-C films and in the liquid phase. These studies have been extended to assist in the identification of astronomical spectra.

A comparison of the composition and structure of carbon films deposited by ns and fs laser ablation of graphite is the subject of this thesis. In addition, the effect of irradiation on the surface of graphite has been investigated in detail. Laser-induced phase transitions from graphite to sp-bonded carbon and trans-polyacetylene chains as well as the formation of nano-diamond have been observed after irradiation with fs pulses. An optical orientation mechanism involving both electric and magnetic interactions is proposed to understand the formation of nano-stripes and other structures on irradiated graphite surfaces. These phenomena are not observed after nanosecond laser irradiation. Tetrahedral carbon (ta-C) films deposited at cryogenic temperatures using ns laser radiation consist of sub-micron graphitized grains embedded in a matrix of sp3-hybridized bonded carbon. Nano-buckling is evident in ta-C films deposited by fs ablation where the composition is found to consist of mixed sp, sp2, and sp3 – hybridized carbons species. It is found that the concentration of sp-bonded chains is negligible in ns-C films. Surface enhanced Raman spectroscopy has been used to characterize molecular species in ns and fs carbon films. Time of flight mass spectroscopy has been used to study plume species produced by laser ablation. It is also found that polyyne molecules can be formed by fs laser dissociation of small molecules in organic solvents. This process is accompanied by the deposition of hexagonal nano-diamond films on substrates placed near the laser focus during irradiation. This opens a new path in the synthesis of 1D conducting molecules and nano-diamond materials for nano-science applications. Quantum chemical calculations involving density functional theory (Gaussian '03) have been carried out in support of this work and have been used to study Raman and IR vibrational modes of several novel carbon molecules synthesized in ta-C films and in the liquid phase. These studies have been extended to assist in the identification of astronomical spectra.

Supramolekulinė chemija – tyrimų kryptis, nagrinėjanti struktūras, sudarytas iš riboto ir neriboto skaičiaus molekulių (tektonų), sąveikaujančių tarpusavyje silpnosiomis nekovalentinėmis sąveikomis. Žinoma, kad medžiagų savybės užkoduotos ne tik molekulių struktūroje, bet ir jų tarpusavio išsidėstyme. Savo ruožtu, chirališkumas yra vienas iš faktorių, leidžiančių vienoms molekulėms atpažinti kitas. Pagrindiniai disertacijos tikslai: nustatyti 1) chiralinių, konformaciškai suvaržytų bei labilių junginių, turinčių biciklo[3.3.1]nonano fragmentą, chromoforų prigimties, tarpusavio orientacijos ir atstumo įtaką chiroptinėms savybėms, 2) chiralinių tripakeistų aromatinių, turinčių biciklo[3.3.1]nonano pakaitus, ir kompleksinių paladžiociklinių junginių chirališkumo ir struktūros įtaką formuojant įvairaus lygio tvarkias supramolekulines struktūras. Naudojantis apskritiminio dichroizmo spektroskopijair teoriškai atliktais ab initio skaičiavimais charakterizuotos molekulės, turinčios įvairios elektroninės prigimties chromoforus, bei jose vykstantys elektroniniai šuoliai. Susintetinti tripakeisti aromatiniai junginiai, turintys išorinius biciklo[3.3.1]nonano ir įvairių dydžių aromatinius fragmentus. Ištirta tokių save atpažįstančių chiralinių tripakeistų aromatinių junginių struktūros įtaka supramolekulinei asociacijai tirpale ir ant paviršiaus. Nustatyta, kad susintetinti V formos chiralinis ir raceminis dialkinbiciklo[3.3.1]nonenil- ligandai, turintys koordinuojantį piridino pakaitą... [toliau žr. visą tekstą] / The supramolecular chemistry of assemblies composed of a limited or infinite number of the molecular tectons interacting with each other via noncovalent interactions was investigated with a special emphasize on the chirality of the building blocks. The following objectives were pursued in this work: 1) to determine the electronic structure of both conformationally rigid and labile chiral bicyclo[3.3.1]nonane compounds, the mutual orientation and distance of the chromophores and its impact on chiroptical properties, 2) to study the influence of chirality and structure of palladacycle and trisubstituted compounds, containing external bicyclo[3.3.1]nonanyl- and aromatic fragments of different size on the formation of various supramolecular structures. The chiral bicyclo[3.3.1]nonane compounds with chromophores of different electronic nature were synthesized. The possibilities of exciton interaction and charge transfer phenomena were studied in the obtained molecules. The influence of chirality and structure of trisubstituted compounds containing external bicyclo[3.3.1]nonanyl- and aromatic fragments of different size on supramolecular association in solution and on the surface was investigated. In solution, the trisubstituted compounds exist in the form of nanoparticles with regular supramolecular structure. It was shown that the V-shaped chiral and racemic dialkynbicyclo[3.3.1]nonenyl- ligands having coordinating pyridine moiety, form rhomb-shaped palladacycle. The racemic and... [to full text]

The supramolecular chemistry of assemblies composed of a limited or infinite number of the molecular tectons interacting with each other via noncovalent interactions was investigated with a special emphasize on the chirality of the building blocks. The following objectives were pursued in this work: 1) to determine the electronic structure of both conformationally rigid and labile chiral bicyclo[3.3.1]nonane compounds, the mutual orientation and distance of the chromophores and its impact on chiroptical properties, 2) to study the influence of chirality and structure of palladacycle and trisubstituted compounds, containing external bicyclo[3.3.1]nonanyl- and aromatic fragments of different size on the formation of various supramolecular structures. The chiral bicyclo[3.3.1]nonane compounds with chromophores of different electronic nature were synthesized. The possibilities of exciton interaction and charge transfer phenomena were studied in the obtained molecules. The influence of chirality and structure of trisubstituted compounds containing external bicyclo[3.3.1]nonanyl- and aromatic fragments of different size on supramolecular association in solution and on the surface was investigated. In solution, the trisubstituted compounds exist in the form of nanoparticles with regular supramolecular structure. It was shown that the V-shaped chiral and racemic dialkynbicyclo[3.3.1]nonenyl- ligands having coordinating pyridine moiety, form rhomb-shaped palladacycle. The racemic and... [to full text] / Supramolekulinė chemija – tyrimų kryptis, nagrinėjanti struktūras, sudarytas iš riboto ir neriboto skaičiaus molekulių (tektonų), sąveikaujančių tarpusavyje silpnosiomis nekovalentinėmis sąveikomis. Žinoma, kad medžiagų savybės užkoduotos ne tik molekulių struktūroje, bet ir jų tarpusavio išsidėstyme. Savo ruožtu, chirališkumas yra vienas iš faktorių, leidžiančių vienoms molekulėms atpažinti kitas. Pagrindiniai disertacijos tikslai: nustatyti 1) chiralinių, konformaciškai suvaržytų bei labilių junginių, turinčių biciklo[3.3.1]nonano fragmentą, chromoforų prigimties, tarpusavio orientacijos ir atstumo įtaką chiroptinėms savybėms, 2) chiralinių tripakeistų aromatinių, turinčių biciklo[3.3.1]nonano pakaitus, ir kompleksinių paladžiociklinių junginių chirališkumo ir struktūros įtaką formuojant įvairaus lygio tvarkias supramolekulines struktūras. Naudojantis apskritiminio dichroizmo spektroskopijair teoriškai atliktais ab initio skaičiavimais charakterizuotos molekulės, turinčios įvairios elektroninės prigimties chromoforus, bei jose vykstantys elektroniniai šuoliai. Susintetinti tripakeisti aromatiniai junginiai, turintys išorinius biciklo[3.3.1]nonano ir įvairių dydžių aromatinius fragmentus. Ištirta tokių save atpažįstančių chiralinių tripakeistų aromatinių junginių struktūros įtaka supramolekulinei asociacijai tirpale ir ant paviršiaus. Nustatyta, kad susintetinti V formos chiralinis ir raceminis dialkinbiciklo[3.3.1]nonenil- ligandai, turintys koordinuojantį piridino pakaitą... [toliau žr. visą tekstą]

Ce manuscrit présente l’utilisation du diisopropylaminoborane comme agent de borylation d’halogénuresd’aryles et de sels d’aryldiazonium. Cet agent de borylation a fait l’objet d’études au sein du laboratoireet de nouvelles méthodologies ont été développées. Une méthodologie générale de borylation de selsde diazonium, catalysée par des métallocènes dérivés du fer, du titane et du zirconium a étédéveloppée, permettant l’accès à des composés d’intérêt comme les halogénures d’aryles borylés. Deplus, une étude cinétique et mécanistique supportée par des calculs théoriques ont permisd’appréhender le mécanisme de cette nouvelle réaction. Une extension de la borylation catalysée aupalladium a été réalisée, permettant l’utilisation de bromures et de chlorures d’aryles ainsi qu’uneméthode de synthèse one-pot de dérivés biaryles non symétriques. Ces méthodes permettent deboryler efficacement des halogénures d’aryles en utilisant une catalyse au palladium homogène ousemi-hétérogène. Enfin, une étude de réactivité entre le diisopropylaminoborane et desorganométalliques dérivés du lithium et du magnésium a été achevée. Une méthodologie généraled’accès aux acides boriniques ainsi qu’une étude mécanistique a été réalisée. / This manuscript describes the use of diisopropylaminoborane as borylating agent of aryl halides anddiazonium salts. This borylating agent has been the subject of studies in the laboratory and newmethodologies has been done. A general methodology of borylation of aryl diazonium salt catalyzed byiron, titanium and zirconium metallocene was developed, allowing access to useful compounds such ashalogenated aryl boron species. Furthermore, kinetic and mechanistic studies supported by theoreticalcalculation allowed a better understanding of the mechanism of the reaction. An extension of thepalladium catalyzed reaction was realized, allowing the use of aryl bromides and chlorides together witha new one-pot unsymetrical biaryl synthesis. Those methods allowed an efficient borylation of arylshalides using homogeneous semi-heterogeneous palladium catalyst. Finally, a study of reactivity of thediisopropylaminoborane and organometallics such as Grignard and organolithium was done. A generalmethodology was developed for the synthesis of diarylborinic acids and a mechanistic study wasachieved.

Les piles à combustibles à électrolyte solide de type SOFC permettent de transformer directement l’énergie de la réaction chimique de formation de l’eau à partir de l’hydrogène et de l’oxygène, en énergie électrique. De nos jours, les apatites de type silicates de terres rares présentent beaucoup d’intérêt comme électrolyte solide en raison de leurs propriétés de transport élevées avec une forte conductivité ionique et une faible énergie d'activation. Ils peuvent fonctionner de manière stable à une température intermédiaire sur une large plage de pression partielle d'oxygène en maintenant d'excellentes performances. Ils sont ainsi considérés comme de bons candidats pour les électrolytes de piles de type IT-SOFC. Parmi cette série de conducteurs, le type La-Si-O possède une conductivité plus élevée et leur performance serait modifiée par différents éléments dopants.L'objectif de cette thèse est d'étudier les effets des éléments de substitution / dopage ainsi que les méthodes de synthèse sur les propriétés structurales ainsi que sur la conductivité des apatites de type silicates de lanthane. Dans cette étude, nous utilisons une double approche: une approche de simulation et une approche expérimentale pour optimiser la pureté et les performances des matériaux d'électrolyte.Dans l'approche de simulation, le calcul basé sur la DFT (Théorie de la fonctionnelle de la densité) a été réalisée en vue d’étudier l'effet des positions de dopage: dopant Sr à La position de La et dopant Ge à la position de Si. Les résultats obtenus par le calcul concernant la conductivité ionique confirment ceux obtenus par l’expérience.Avec l’approche expérimentale, nous présentons la synthèse et la caractérisation de La10Si6O27 (LSO) dopé par Sr et élaboré par des procédés sol-gel. Les résultats montrent que la conductivité ionique est activé thermiquement et que les valeurs se situent entre 4,5 × 10-2 et 1 x 10-6 S·cm-1 à 873 K et dépend des conditions d’élaboration et de la composition de la poudre. / The Solid Oxide Fuel Cell (SOFC) defined by its ceramic and oxide electrolyte, is an electrochemical energy conversion device that produces electricity directly from the chemical reaction of fuel. Nowadays, apatite type rare earths silicates and germaniums attract many interests as the solid electrolyte due to the superior transport properties with high ionic conductivity and low activation energy. They can operate stably at intermediate temperature over a wide oxygen partial pressure range and maintain excellent performances, being considered as a candidate for IT-SOFC electrolytes. Among this series of conductors, the La-Si-O type has a higher conductivity and the performance would be modified by different doping elements.The objective of this thesis is to study the effects of element substitution/doping and synthesis methods on the structural and conductivity properties of apatite type lanthanum silicates. In this study, we use a double approach: a simulation approach and an experimental approach to optimize the electrolyte materials purity and performance.Using simulation approach, a first principle calculation based on DFT (Density Functional Theory) was carried out to investigate the effect on doping positions: Sr dopant at La position and Ge dopant at Si position. The calculation results give a connection to the ionic conductivity obtained by experiments.With experimental approach, we present the synthesis and characterization of Sr-doped La10Si6O27 (LSO) prepared through an optimized water-based sol-gel process. The results show that the ionic conductivity is thermally activated and values lies between 4.5×10-2 and 1×10-6 Scm-1 at 873 K as a function of the composition and powder preparation conditions.

Corrosion of metallic materials is a natural process, and our study shows that even in an alkaline environment severe corrosion may occur on a carbon steel surface. While corrosion cannot be stopped it can be retarded. Many of the traditional anti-corrosion approaches such as the chromate process are effective but hazardous to the environment and human health. Mefp-1, a protein derived from blue mussel byssus, is well known for its extraordinary adhesion and film forming properties. Moreover, it has been reported that Mefp-1 confers a certain corrosion protection for stainless steel. All these facts indicate that this protein may be developed into corrosion inhibitors with ‘green’, ‘effective’ and ‘smart’ properties. In this study, a range of surface-sensitive techniques have been used to investigate adsorption kinetics, film forming and film compaction mechanisms of Mefp-1. In situ atomic force microscopy (AFM) enables the protein adsorption on substrates to be visualized, whereas the ex situ AFM facilitates the characterization of micro- and nano-structures of the protein films. In situ Peak Force AFM can be used to determine nano-mechanical properties of the surface layers. The quartz crystal microbalance with dissipation monitoring (QCM-D) was used to reveal the build-up of the Mefp-1 film on substrates and measure the viscoelastic properties of the adsorbed film. Analytical techniques and theoretical calculations were applied to gain insights into the formation and compaction processes such as oxidation and complexation of pre-formed Mefp-1 films. The electron probe micro analyzer (EPMA) and X-ray photoelectron spectroscopy (XPS) were utilized to obtain the chemical composition of the surface layer. Electrochemical impedance spectroscopy (EIS) measurements were performed to evaluate the corrosion inhibition efficiency of different forms of Mefp-1 on carbon steel substrates. The results demonstrate that Mefp-1 adsorbs on carbon steel surfaces across a broad pH interval, and it forms a continuous film covering the substrate providing a certain extent of corrosion protection. At a higher pH, the adsorption is faster and the formed film is more compact. At neutral pH, results on the iron substrate suggest an initially fast adsorption, with the molecules oriented preferentially parallel to the surface, followed by a structural change within the film leading to molecules extending towards solution. Both oxidation and complexation of the Mefp-1 can lead to the compaction of the protein films. Addition of Fe3+ induces a transition from an extended and soft protein layer to a denser and stiffer one by enhancing the formation of tri-Fe3+/catechol complexes in the surface film, leading to water removal and film compaction. Exposure to a NaIO4 solution results in the cross-linking of Mefp-1, which also results in a significant compaction of the pre-formed protein film. Mefp-1 is an effective corrosion inhibitor for carbon steel when added to an acidic solution, and the inhibition efficiency increases with time. As a film-forming corrosion inhibitor, the pre-formed Mefp-1 film provides a certain level of corrosion protection for short term applications, and the protection efficiency can be significantly enhanced by the film compaction processes. For the long term applications, a thin film composed of Mefp-1 and ceria nanoparticles was developed. The deposited Mefp-1/ceria composite film contains micro-sized aggregates of Mefp-1/Fe3+ complexes and CeO2 particles. The Mefp-1/ceria film may promote the further oxidation of ferrous oxides, and the corrosion resistance increases with time. Moreover, phosphate ions react with Fe ions released from the surface and form deposits preferentially at the surface defect sites. The deposits incorporate into the Mefp-1/ceria composite film and heal the surface defects, which result in a significantly improved corrosion inhibition effect for the Mefp-1/ceria composite film in both initial and prolonged exposure situations / <p>QC 20130610</p>

Le système spirocyclique (7,5) est un motif récurrent dans un certain nombre de produits naturels tels que les Micrandilactones ou les Rubriflordilactones. Ces structures polycycliques représentent un réel défi synthétique pour les chimistes organiciens puisqu'elles présentent au moins neuf centres stéréogènes dont plusieurs sont quaternaires. L'objectif principal de ce travail était de développer de nouvelles réactions de cycloaddition [3+2] et de les utiliser comme étape clé afin d'obtenir rapidement et efficacement le squelette polycylique de ces composés. La première partie de ces travaux a été consacrée au développement d'une réaction de cycloaddition [3+2] intra- et intermoléculaire mettant un jeu un nouveau partenaire dipolarophile, les γ-alkylidènes-buténolides. Cette étape clé conduit à la formation de cycloadduits hautement fonctionnalisés de façon rapide et efficace avec d'excellents rendements et de façon hautement chimio-, régio- et diastéréosélective. De plus, des calculs théoriques ont permis d'appréhender le mécanisme réactionnel entre un 2-diazo-1,3-cétoester et la protoanémonine catalysé par un sel de rhodium mis en jeu dans ce type de processus et ainsi d'expliquer les résultats obtenus.Dans une deuxième partie, deux approches aux cœurs ABC et CD de la micrandilactone C ont été développées mettant respectivement en jeu une cycloaddition [3+2] formellement intermoléculaire utilisant un lien de type acétal de silicium et suivie par une réaction de Diels Alder. Ainsi, le motif tétracyclique devrait être rapidement accessible après quelques aménagements de la voie de synthèse initiale. / The spiro (7, 5) ring system is a recurring structural moiety in numerous natural products such as Micrandilactones and Rubriflordilactones. In term of complexity, these polycyclic structures represent a synthetic challenge for organic chemist. Indeed, these molecules present at least nine stereogenic centres including several quaternary ones. The main goal of this work was to use unprecedented partners in the [3+2] cycloaddition reaction to obtain quickly and efficiently the polycyclic core of those natural products. The first part of these studies was dedicated to the development of an intra- and intermolecular [3+2] cycloaddition using for the first time a γ-alkylidene-butenolide dipolarophile. This approach provides rapid and facile access to highly functionalised polycyclic molecules along with excellent regio-, chemo- and stereoselectivities. In addition, thanks to computational studies an overall picture of the mechanism of the intermolecular rhodium catalysed [3+2] cycloaddition between 2-diazo-1,3-ketoester and protoanemonin was apprehended, and experimental results have been rationalised.Finally, two approaches to the ABC and CD cores of Micrandilactone C were developed using respectively a formal intermolecular [3+2] cycloaddition reaction in presence of a silicon acetal linker followed by a Diels Alder reaction. The ACDE tetracyclic moiety should be quickly accessible after few modifications of the initial strategy.

La conception et l’élaboration de nouveaux ligands en chimie organométallique évoluent vers le design de ligands multifonctionnels afin d’augmenter l'affinité ligand/métal/substrat et de mimer les catalyseurs de la nature comme les enzymes, en activant de manière synergique les différents partenaires de la réaction. Il existe dans la littérature très peu d’exemples de complexes organométalliques présentant une fonctionnalité acide de Lewis. Dans notre étude, nous avons opté pour l’utilisation d’un atome de bore trivalent pendant. Malgré la forte utilisation des dérivés du bore en catalyse acide de Lewis pour l’activation de divers électrophiles, la conception de tels ligands ambiphiles, pour des complexes organométalliques, a été peu décrite et la réactivité peu étudiée. Ce travail a donc pour but d’explorer et de valider la viabilité de leurs préparations et de leurs utilisations.La première partie de ces travaux a été consacrée au développement de nouveaux complexes bifonctionnels métal/NHC/ester boronique pendant de Pd(II), Rh(I), Ru(II), Au(I) et Cu(I) et leurs applications en catalyse, afin d’accéder à de nouveaux modes d’activation de petites molécules.Dans la deuxième partie, un nouveau mode d’activation efficace de la liaison B-H des carbènes boranes incorporant un bras allylique ou homoallylique par des complexes de rhodium pour accéder à une famille de NHC-boranes cycliques énantioenrichis a été développé.Enfin, la troisième partie constitue la synthèse des travaux sur deux nouvelles familles de cations boronium macrocycliques et leurs applications dans la reconnaissance des anions. / Conception and elaboration of new ligands in organometallic chemistry evolved towards the design of multi-functional shape to increase the affinity ligand/metal/substrate to mimic nature’s catalysts, and to promote, in most cases, an increasing reactivity and selectivity in the catalytic process. Despite the significant development of N-heterocyclic carbene (NHC) ligands in organometallic chemistry since the last decade, complexes bearing pendant trivalent boron derivatives were so far overlooked.In this context, bifunctional ligands containing NHC and boron moieties have been developed and the corresponding Ag(I), Pd(II), Rh(I), Cu(I) and Ru(II) complexes were designed and prepared for a synergistic activation of both reaction partners by the metal center and the pendant Lewis acidic boron atom.During this work, B−H bond activation of NHC-boranes by a diphosphane-ligated cationic Rh complex was applied in an unprecedented intramolecular enantioselective hydroboration of simple olefins. This study led to a library of enantioenriched cyclic boranes in high yields (up to 94%) with high regio- (up to 100%) and enantioselectivities (er up to 99.2:0.8).As part of this work, new boronium macrocycles were synthesized in high yields and their anion binding ability was evaluated by fluorimetric and 1H NMR titration. These new macrocycles display high binding affinity for halides and oxoanions in the solid state, in solution and in the gas phase.