In der vorliegender Arbeit wurde die photochemische Bildung der Acridiniumionen in einem Pseudorotaxan und die daraus resultierende Transformation der Lichtenergie in die Translationsenergie, was als erster Schritt in Richtung der molekularen Maschinen angesehen wird, untersucht. 9-Phenyl-9-hydroxyacridan unterscheidet sich in ihrer Lichtabsorption, Molekülgeometrie und Elektronen- Donatorstärke gravierend von den korrespondierenden Acridiniumionen. Die Änderung der elektronischen Eigenschaften bei der Umwandlung der Acridane- in die Acridinium ist daher potentiell nutzbar, um nichtkovalente Bindungskräfte in supramolekularen Einheiten zu beeinflussen. Ziel der vorliegenden Arbeit war die Erschließung eines neuen Zugangs zu linearen und makrocyclischen Systemen, die als Strukturelement eine Acridaneinheit besitzen. Die Makrocyclen mit elektronenreichen 9-Phenylacridanbausteinen wurden unter high-dilution-Bedingungen erhalten. Bei der Photoanregung wurden unter Abspaltung von Methoxidionen die elektronenarmen korrespondierenden Acridiniummakrocyclen gebildet. Die Photoheterolyse findet in alkoholischen Lösungsmitteln, Acetonitril und in Toluol statt. Die Lebensdauer des Acridiniummethoxids kann durch Mischen des Alkohols mit dem Acetonitril gesteuert werden. Auch nach zehn Schaltcyclen ist keine Ermüdung des Systems festzustellen. Als molekulare Fäden kommen für die neuen Makrocyclen entweder Moleküle mit elektronenarmen Erkennungstationen für die Acridanverbindungen oder elektronenreiche Erkennungsstationen für die Acridiniumringe in Frage. Es wurden zahlreiche Untersuchungen zur Komplexierung der neuen Makrocyclen mit Hilfe der spektroskopischen Titrationen durchgeführt. Dabei wurde das photoschaltbare Pseudorotaxan gefunden. Im Rahmen dieser Arbeit wurde ein neuer langlebiger Photoschalter optimiert und mit Hilfe der 1H-NMR-Spektroskopie wurde die durch Licht injizierte molekulare Bewegung beobachtet. / For this work we have examined the photolytic formation of acridinium ion within pseudorotaxanes and the resulting transformation of light energy into translational movement. This can be regarded as the first step towards (creating a) molecular machine. 9-phenyl-9-methoxyacridane distinguishes itself from its corresponding acridinium ions in terms of light absorption, shape, and electronic donor strength. The acridane can be regarded as candidates for photoswitching supramolecular units, because they can be transformed into positively charged acridinium ions. These ions generate an electron acceptor from an electron donor. The object of the following thesis is the development of a new synthetic approach to linear or makrocyclic systems, which contain acridane as a structural element. Macrocycles with electron-rich 9-phenyl-9-methoxyacridan units were prepared under high dilution conditions. The acridinium macrocycles are generated by photoheterolysis of this methoxy derivative, which has a thermal response to acridane macro cycles, thus closing the switching cycle. Heterolytic photodissociation occurs in alcohols, acetonitrile and toluene. Mixing alcohol with acentonitril can control the lifespan of the acridinium methoxide. Even after 10 switching cycles the system seemed unaffected. The molecular thread and macrocycles must be complementary in that they can interact by attracting forces, through generating an electron acceptor from an electron donor. The complex formation of acridan macrocycles with electron acceptor molecular thread was studied using spectrophotometric titration. As a result, photoswitchable pseudorotaxane was formed between acridan crown ethers and (2,2-bipyridine) molecular thread. In the context of this research, we have found that such a transformation is possible. A new, durable photoswitch has been developed, and using the 1H-NMR-spectroscope, we observed the molecular movement, which was made visible through the application of light.

A química supramolecular representa o caminho mais promissor na rota de desenvolvimento da nanotecnologia devido à maneira especial com que diferentes moléculas interagem, trocando informações e criando estruturas organizadas. Esta tese pretende contribuir para este campo de pesquisa, através do estudo de três derivados terpiridínicos funcionalizados e seus complexos de ferro(II): 4\'-(3- tienil)- 2,2\':6\',2\'\'-terpiridina (titpy), [Fe(titpy)2]2+; 4\'-(4\'-(fenil)- 2,2\':6\',2\'\'-terpiridina (phtpy), [Fe(phtpy)2]2+ e 4\'-(4-bromo-fenil)-2,2\':6\',2\'\'-terpiridina (Br-phtpy), [Fe(Brphtpy)2]2+. A investigação desses complexos foi realizada por métodos espectroscópicos, físico-químicos e computacionais. As propriedades dos complexos sintetizados foram exploradas empregando o conceito de química supramolecular, através da interação dos mesmos com β-ciclodextrina, matriz de gel de pentóxido de vanádio e nanopartículas de ouro. Os novos materiais gerados apresentaram características que tornam possível a sua aplicação em diferentes áreas como: dosimetria UV-Vís, materiais para baterias e armazenamento de cargas e nanoestruturas organizadas. / Supramolecular chemistry is the most promising path on the development of nanotechnology. This is due to the special way that different molecules interact, exchanging information and generating organized structures. This PhD thesis intends to contribute in the supramolecular research field, with the study of three functionalized terpyridines derivates and the correlated iron(II) complexes: 4\'-(3-thienyl)-2,2\':6\',2\'\'-terpyridine, (titpy), [Fe(titpy)2]2+; 4\'-(4\'-(phenyl)- 2,2\':6\',2\'\'-terpirydine (phtpy), [Fe(phtpy)2]2+ and 4\'-(4-bromophenyl)-2,2\':6\',2\'\'- terpirydine (Br-phtpy), [Fe(Br-phtpy)2]2+. The investigations of the prepared compounds were done by spectroscopy, physicochemical and computational methods. The properties of the synthesized complexes were exploited in the supramolecular chemistry sense by the interactions of those compounds with α-cyclodextrin, vanadium pentoxide gel matrix and gold nanoparticles. The originated materials presented features that make possible the employment of them in distinct areas such: UV-Vis dosimeter, batteries and charge storage, and organized nanostructures

We present the synthesis and characterisation of novel single organic molecules known as phenoxylene borazines and borazatruxenes. Using temperature-dependant and concentration-dependant 1H NMR, we probe the supramolecular aggregation of these molecules in solution. Finally, we synthesise 2D hybrid material comprised of electron delocalised benzene rings and electron localised borazine rings. Using a combination of solid-state 11B and 13C NMR techniques, Raman spectroscopy and XPS, we confirm the presence of benzene and borazine regions in these novel materials.

A preparação, caracterização e estudo de propriedades moleculares e supramoleculares de meso-tetrapiridilporfirinas modificadas com quatro complexos de cloro(bipiridina) platina(II) ligados às posições meta e para de ligantes piridínicos periféricos, foi objetivo desta tese. As supermoléculas isômeras foram isoladas no estado sólido e extensivamente caracterizados por meio de espectroscopia UV/VIS, FT-IR e RMN de Pt-195, assim como através de TGA e espectrometria de massa com ionização por spray de elétrons, ESI-MS, e técnicas de dissociação induzidas por colisão. Medidas de voltametria cíclica e de espectroeletroquímica foram realizadas para caracterizar os estados redox da porfirina central e dos complexos periféricos, mostrando uma semelhança entre as duas formas isômeras. A maior diferença, entretanto, foi observada nas suas propriedades estruturais, diagnosticadas por modelagem molecular, e refletidas na morfologia dos filmes obtida por meio de técnicas de microscopia de varredura por sonda, SPM, e através da associação com filmes de DNA, monitorada com o auxílio de técnicas de espectroscopia eletrônica e ressonância plasmônica de superfície, SPR. No último caso, o DNA foi imobilizado sobre a superfície do sensor de ouro, usando aminotióis adequados, sendo que a interação do isômero meta conduziu a uma resposta contrastante, relevando uma forte ligação com a cadeia do DNA, provavelmente nas proximidades das fendas estruturais menores desse biopolímero. A interação do isômero para com o DNA foi demasiadamente fraca para ser observada por meio de SPR. A associação molecular das porfirinas tetraplatinadas catiônicas com ftalocianinas aniônicas tetrassulfonadas conduziu à formação de pares iônicos em solução. O filme do isômero para imobilizado sobre eletrodo de carbono vítreo apresentou atividade na redução eletrocatalítica de nitrito. Os trabalhos realizados demonstraram que os novos sistemas supramoleculares derivados de porfirinas e complexos de platina proporcionam interessantes materiais híbridos inorgânico-biológicos contendo DNA e metais nobres, com potenciais aplicações em terapia fotodinâmica, sensoriamento e em dispositivos moleculares. / The synthesis, characterization and investigation of the molecular and supramolecular behaviour of meso-tetrapyridylporphyrins containing four chloro(bipyridine) platinum(II) complexes attached at the meta and para positions of the peripheral pyridine ligands is focused on this thesis. The isomeric supermolecules were isolated in the solid state, and extensively characterized by means of UV-visible, FT-IR and 195Pt NMR spectroscopy, as well as, by TGA and electrospray spectrometry associated with collision induced techniques. Cyclic voltammetry and spectroelectrochemical measurements were performed to characterize the redox sites on the porphyrin and peripheral complexes, revealing a close similarity between the two isomeric supermolecules. Major differences were observed on their structural properties, as demonstrated by means of molecular simulations, and by the morphology of the molecular films probed by SPM techniques, and also by their association with DNA films, which was monitored by means of SPR techniques. In the last case, DNA was first immobilized onto the surface of the gold sensor, using suitable aminothiols and the interaction of the meta-isomer led to a contrasting response, exhibiting a strong binding to the DNA chain, presumably at the proximity of the minor grooves. The interaction of the para-isomer with DNA was too weak to be probed by means of the SPR technique. Molecular association of the tetraplatinum porphyrin species, with tetrasulphonated phtalocyanines, leading to ion pairs in solution, was also investigated. The molecular film of the para-isomer immobilized over glass carbon electrode has shown activity in the electrocatalytic reduction of nitrite. This work on the supramolecular porphyrin platinum species provided new interesting approaches for generating hybrid biological-inorganic systems, containing DNA and noble metals, for sensing applications, and molecular devices.

Compostos porfirínicos desempenham uma grande variedade de funções em sistemas biológicos. Em particular, no processo de respiração e na fotossíntese, dois ou mais macrociclos porfirínicos encontram-se próximos na mesma estrutura protéica. A proximidade e a orientação entre os macrociclos são importantes no tipo de função desempenhada; a disposição cofacial entre os macrociclos é um dos fatores responsáveis pelo processo de transferência de elétrons que ocorre nos fotossistemas de organismos fotossintetizantes. Vários estudos têm sido realizados in vitro, com o objetivo de entender o efeito da proximidade e orientação entre os macrociclos nos processos de transferência eletrônica fotoinduzida que ocorrem durante a fotossíntese. Uma das maneiras de construir sistemas miméticos capazes de armazenar luz e transferir elétrons consiste na formação de pares iônicos entre moléculas que apresentam cargas opostas. Apesar da maior versatilidade desses sistemas, não existem estudos sistemáticos que avaliem os efeitos estruturais provenientes da funcionalização dos macrociclos porfirínicos no processo de formação e nas propriedades espectroscópicas de pares iônicos. Esse trabalho apresenta um estudo sobre a formação de pares iônicos entre metaloftalocianinas aniônicas e uma nova classe de porfirinas catiônicas planares e não planares. Através da determinação dos valores das constantes de formação dos heterodímeros, procurou-se avaliar como as características estruturais/eletrônicas dos substituintes β- e meso- do anel se refletem no processo de formação e nas propriedades espectroscópicas dos agregados. Esses estudos foram realizados em diferentes solventes/misturas de solventes e em diferentes forças iônicas, de modo que foi possível avaliar como a mudança do solvente ou da concentração de eletrólito adicionado se reflete no processo de associação entre espécies de carga oposta. As porfirinas não planares utilizadas derivam de uma classe de porfirinas planares que apresentam grupos benzílicos substituídos ligados aos grupos piridínicos presentes nas posições mesa do macrociclo porfirínico; oito átomos de bromo ligados nas posições β-pirrólicas do macrociclo causam a distorção do anel. A introdução de 8 átomos de bromo nas posições β-pirrólicas do macrociclo porfirínico provoca alterações nas propriedades espectroscópicas e fotofísicas das porfirinas, comparando-se as porfirinas β-octabromadas e seus respectivos análogos não bromados. Essa alterações são decorrentes, tanto da distorção do anel, como do efeito de átomo pesado exercido pelos átomos de bromo. Como principais alterações pode-se citar: (i) deslocamento batocrômico dos máximos de absorção e emissão; (ii) redução significativa nos valores de Φfl; (iii) maiores deslocamentos de Stokes; (iv) diminuição nos valores dos tempos de vida do estado excitado triplete; e (v) em função do tipo de solvente empregado, observa-se a coexistência de duas espécies distintas no estado excitado triplete que decaem com tempos de vida distintos. Os valores de KPI obtidos demonstraram que a associação entre as porfirinas catiônicas e as ftalocianinas aniônicas é dependente de uma série de fatores, e pode ser modulada alterando-se o tipo de substituinte ligado ao macrociclo porfirínico e as características do meio, tais como o tipo de sol vente empregado e a força iônica do meio. Os estudos de associação realizados em DMSO demonstraram que (i) a presença do resíduo benzílico traz interações hidrofóbicas adicionais significativas ao processo de associação; (ii) o impedimento estérico decorrente do maior volume do meso-substituinte predomina sobre os efeitos eletrônicos dos grupos ligados na posição para do anel benzílico; e (iii) diferenças na magnitude da distorção da ligação Ni-N e Cu-N para fora do plano, em função da ligação axial a uma molécula de DMSO, se refletem nos valores de KPI. A partir dos estudos realizados em diferentes misturas de solventes, pôde-se constatar que (i) mudanças na esfera de solvatação das porfirinas em meios com maior concentração de H2O alteram os valores de KPI ao longo da série de porfirinas estudadas; e (ii) a formação de dímeros de ftalocianina compete com a formação do heterodímero ftalocianina/porfirina. O controle da força iônica do meio produz alterações significativas nos valores de KPI ao longo da série de porfirinas estudadas. A partir desses experimentos foi possível avaliar o efeito eletrônico dos grupos ligados na posição para do anel benzílico no processo de associação com as ftalocianinas, em relação à ZnTMPyP. A introdução de átomos de bromo no macrociclo porfirínico produz uma série de alterações no processo de associação entre as porfirinas e as ftalocianinas. Durante a associação entre as ftalocianinas e as Zn(II)porfirinas β-octabromadas que apresentaram maiores desvios com relação à planaridade do anel, observou-se a formação de uma espécie trimérica constituída por duas moléculas de porfirina e uma molécula de ftalocianina. Uma vez que ambos os macrociclos encontram-se coordenados axialmente a uma molécula de DMSO, que inviabiliza a formação de um trímero onde os macrociclos se encontram dispostos cofacialmente, este trímero deve ser formado a partir de uma sobreposição parcial entre os macrociclos de carga oposta. Os estudos de fluorescência demonstraram que ocorre uma eficiente supressão da fluorescência da Zn(II)porfirina após a adição de ftalocianina no meio. Demonstraram ainda que esta supressão ocorre através de um processo estático, devido à formação de um complexo de estado fundamental. A avaliação preliminar dos resultados obtidos durante a caracterização do estado excitado triplete dos heterodímeros CuPcTS/ZnP indica que a espécie transiente monitorada na região de 700nm corresponde ao heterodímero presente em solução. Indica ainda que o estado excitado triplete do heterodímero apresenta um caráter de energia predominantemente da ftalocianina. / Macrocyclic tetrapyrroles, like porphyrin derivatives, occur biologically in many enzymes, heme compounds, and photosynthetic protein as chlorophyll. Particularly in the latter, two chlorophylls adopt a face-to-face conformation to form the so-called special pair, the efficient primary electron-donor in the photosynthetic apparatus. It is known that the cofacial arrangement of chlorophylls is a very important feature, because photosynthetic electron transfer process is a function of macrocycle separation and orientation. The complexity of this process has prompted numerous studies of pairing donor-acceptor molecules to mimic the photosynthetic system and understand how the spatial orientation and proximity between the macrocycles affect the fotoinduced electron transfer process. Spontaneous aggregation between porphyrins and phthalocyanines bearing charged peripheral substituents occurs in solution, and thus, these molecules have been employed to study face-to-face heterodimer bound electrostatically. Despite the fact that these systems share many of the characteristics of naturally occurring special pair, there is no systematic study assessing the structural effects of functionalized porphyrin rings on the association process for anionic macrocycles. This work reports a heterodimer formation between anionic phthalocyanines and a new class of cationic planar and non planar porphyrins. Heterodimers have been characterized by determining the formation equilibrium constants (KPI) in different media and ionic strength. The new class of non planar cationic Zn (II) porphyrins synthesized presents eight bromine atoms attached to the β-pyrrole position of the porphyrin ring, leading to a high degree of distortion. The planar cationic precursor presents substituted benzylic groups attached to the nitrogen atoms of the pyridyl residues located at the meso-porphyrin positions. Both ring distortion and heavy atom effect caused by the introduction of bromine atoms at the macrocycle periphery cause many changes in the spectroscopic and photophysical properties, comparing to the planar precursor. The main differences observed are: (i) batochromic shifts of absorption and emission maxima; (ii) lower fluorescence quantum yields; (iii) larger Stokes shifts; (iv) reduced triplet lifetimes and; (v) depending on the solvent employed, it was observed the coexistence of two distinct species in the excited triplet state that posses different lifetimes. According to the KPI values obtained, it was inferred that the association process can be modulated by changing the meso- and β-substituent attached to the porphyrin ring, and altering medium characteristics. The KPI values obtained in DMSO solution suggest that steric hindrance from benzylic groups overwhelms the additional hydrophobic/eletronic effects from these meso-substituents. When the ionic strength was kept constant, a decrease in the KPI values was observed, as expected to the association between ionic species. It could be noted, therefore, that the additional hydrophobic contribution from benzylic substituent, and also the electronic characteristics of the small groups attached to the benzylic ring affect the association process. From experiments carried out in solvent mixtures, it could be observed that, if the solvent dielectric constant increases, the KPI values decrease. Likewise, changes in the porphyrin macrocycle solvation alter the KPI value through the porphyrin serie studied. Additionally, as the water concentration increases, the phthalocyanine self-association process competes with heterodimer formation. The introduction of bromine at ring periphery changes the association process. The KPI values obtained to the heterodimer formed between the anionic phthalocyanines and the β-octabrominated porphyrins, are about 10 times smaller compare d to the KPI obtained using the planar precursor. It is a consequence of nonplanar distortion, that diminishes the cofacial approximation between the macrocycles. Addi tionally, heterotrimers can be formed by altering the porphyrin concentration - this behavior was not found to the aggregates formed between the phthalocyanines and the planar precursor derivatives at the same condition. Emission studies evidence a ground state complex formation, since the phthalocyanine quenches the Zn (II) porphyrin fluorescence through a static process. The preliminary results obtained to the heterodimer triplet characterization showed that the heterodimer excited triplet state is more delocalized on the phthalocyanine moiety.

Les cucurbiturils (CBn) sont des molécules-cages synthétiques constituées d’un nombre n d’unités glycoluril et dont les applications en chimie, en biologie et en physique ont commencé à être exploitées au début des années 2000. Ces composés trouvent leur importance dans un grand nombre de domaines incluant la chimie en phase solide, le piégeage des contaminants en solution, la catalyse ou encore l’encapsulation de principes actifs pour des applications pharmaceutiques futures. Ces récentes molécules-cages rejoignent le large groupe des récepteurs synthétiques comprenant les cyclodextrines, les calixarènes, les cryptophanes, les carcérands et hémicarcérands. L’encapsulation des gaz dans ce type de structures est encore mal connue à l’heure actuelle et, dans ces travaux de thèse, notre intérêt s’est porté sur la complexation de gaz, notamment de xénon, dans les cucurbiturils. Ces travaux ont débuté par la synthèse de nouveaux cucurbiturils hydrosolubles dans le but d’étudier leur capacité d’encapsulation des gaz rares et de petits alcanes comme le méthane et l’éthane, notre objectif final étant de définir de nouvelles règles régissant l’encapsulation des gaz par les cucurbiturils. Les gaz rares allant de l’hélium au krypton ont été étudiés. Parmi ces gaz, le xénon hyperpolarisé a particulièrement retenu notre attention du fait de son intérêt dans la conception de biosondes pour le développement de nouvelles méthodes de diagnostic en IRM. Dans ce mémoire, la synthèse de nouveaux cyclohexylcucurbiturils mixtes hydrosolubles et leurs études en présence de xénon sont rapportées. Un nouveau cucurbituril mixte constitué de cinq unités glycoluril et d’une unité glycoluril à six chaînons a également été synthétisé. Les deux premiers chapitres constituent une introduction au phénomène d’encapsulation des gaz ainsi que des généralités sur la famille des cucurbiturils. Le troisième chapitre est consacré aux résultats obtenus au laboratoire sur la synthèse de nouveaux composés. Dans un quatrième chapitre, nous avons développé une méthode permettant la préparation de précurseurs d’analogues acycliques de cucurbiturils. Pour cela, la réaction de métathèse par ouverture de cycle associée à la métathèse croisée (ROM-CM) a été utilisée pour mener à bien cette synthèse. Enfin, un cinquième chapitre est consacré aux résultats concernant l’étude de l’encapsulation de gaz dans les nouveaux cucurbiturils synthétisés, étude effectuée en collaboration avec le Laboratoire de Structure et Dynamique par Résonance Magnétique du CEA de Saclay. / The cucurbituril family (CBn) constitutes a group of recent synthetic host-molecules. These compounds are formed by n glycoluril units and, since the beginning of the 2000’s, they have found their interest in multiple domains such as biology, chemistry and physics. They have joined the large group of synthetic receptors comprising cyclodextrins, calixarens, cryptophanes, carcerands and hemicarcerands. Gaz encapsulation in this family of compounds is misunderstood. In these PhD works, our interest concerned gaz complexation, especially xenon, into cucurbiturils. First, the synthesis of new hydrosoluble cucurbiturils to study their ability to encapsulate noble gaz and small alcans such as methan and ethan is described. Our final goal will be to define new rules concerning gaz encapsulation by cucurbiturils. Noble gaz from helium to krypton have been studied. Among these noble gaz, xenon is particularly interesting in the domain of biosensing, for the design of new diagnostic methods by MRI. In this manuscript, the synthesis of a family of hydrosoluble cyclohexylcucurbiturils and their ability to encapsulate xenon is described. Another new cucurbituril constituted by five glycoluril units and one glycoluril unit forming a six-membered ring, has also been prepared. The first two parts of the manuscript present the gaz encapsulation and the cucurbituril family. The third part describes our results concerning the new synthetized cucurbiturils. In the fourth part, we have developped a method based on metathesis reactions (ROM-CM) for preparing some precursors of acyclic congeneers of cucurbiturils. Lastly, the fifth part concerns results about gaz encapsulation. All of this study has been driven in collaboration with Laboratoire de Structure et Dynamique par Résonance Magnétique (CEA Saclay).

Uma nova série de metaloporfirinas supermoleculares não-planares foi obtida por meio de automontagem coordenativa de meso tetra(3-piridil)porfirinas e complexos de rutênio polipiridina ([Ru(bipy)2Cl]+ e [Ru(bipy)2(OH2)]2+). Suas propriedades estruturais e eletrônicas foram investigadas por espectroscopia eletrônica, espectrometria de massas, voltametria cíclica e espectroeletroquímica. As influências do acoplamento eletrônico e da mudança da geometria molecular também foram avaliados, tanto no estado gasoso quanto em solução, e os resultados, comparados com a série de isômeros planares obtidos através da coordenação de complexos de rutênio polipiridina as meso tetra(4-piridil)porfirinas. Nanomateriais eletrostaticamente montados, camada por camada, com derivados aniônicos de porfirinas e ftalocianinas foram elaborados. As propriedades eletrocatalíticas dos mesmos foram investigadas, frente a substratos de interesse como nitrito e sulfito. Efeitos supramoleculares conformacionais e eletrônicos foram observados, tanto em solução quanto nos filmes dos nanomateriais porfirínicos supramoleculares. Verificou-se também, uma influência significativa do pH e do íon metálico coordenado à porfirina nos processos de oxidação e de redução de nitrito e de sulfito. / A new series of nonplanar supermolecular metalloporphyrins have been obtained by coordenative self-assembly of meso-tetra(3-pyridyl)porphyrins and ruthenium complexes such as [Ru(bipy)2Cl]+ and [Ru(bipy)2(OH2)]2+. The electronic and structural properties have been investigated by electronic spectroscopy, mass spectrometry, cyclic voltammetry, and spectroelectrochemistry. The effects of the electronic coupling and molecular geometry on the molecular and nanomaterials properties were investigated in the gas phase and in solution. All results were compared with that obtained for the planar isomers obtained by the coordination of four [Ru(bipy)2Cl] groups to the meso-tetra(4-pyridyl)porphyrins. New nanomaterials were obtained by layer-by-layer electrostatic assembly of those supermolecular cationic porphyrins and tetrasulfonated porphyrins or phthalocyanines. The electrocatalytic properties were investigated for nitrite and sulfite. Electronic and supramolecular conformational effects were observed for those species in solution and in films of the nanomaterials. Moreover, a significant effect of the pH and of the transition metal ion coordinated to the porphyrin ring on the electrocatalytic activity were also observed.

Les hémicryptophanes, molécules constituées d’une unité cyclotriveratrylène (CTV) reliée à un autre groupement de symétrie C3, sont des molécules cages qui trouvent de nombreuses applications dans le domaine de la chimie hôte-invité. Dans une première partie, ce manuscrit présente une revue des développements récents de la chimie des hémicryptophanes et définit les objectifs de ce travail de thèse.Nos travaux concernent principalement le design d'hémicryptophanes spécifiquement conçus pour la reconnaissance moléculaire de substrats d'intérêt. Ainsi, des structures variées d'hémicryptophanes ont été conçues comme capteur fluorescent du phosphate de choline, ou pour la reconnaissance de paire d'ions. Des hémicryptophanes hétéroditopiques originaux portant des unités tris(2-pyridylmethyl)amine (TPA) ont été synthétisés et présentent un grand intérêt pour des applications ultérieures en reconnaissance. Nous avons étudié la reconnaissance stéréosélective de saccharides avec des hémicryptophanes énantiopurs qui associent trois types de chiralité sur sept centres stéréogènes. Enfin, nous décrivons le mouvement de "respiration" moléculaire de cages énantiopures, enrichissant ainsi les rares applications des hémicryptophanes comme machines moléculaires.Des complexes du vanadium(V) des hémicryptophanes ont été développés comme catalyseurs efficaces dans des réactions de sulfoxydation et pour l'oxydation catalytique de lignines. Des dérivés azaphosphatrane d’hémicryptohanes ont été développés comme organocatalyseurs de la réaction de polymérisation par ouverture du lactide. La dernière partie de ce manuscript est consacrée à des développements nouveaux dans le domaine de la formation de cages par auto-assemblage. Nous avons réussi à former par coordination des tétraèdres dont les quatre faces comportent une sous-unité azaphosphatrane. Nous montrons pour la première fois que dans ce type de cage l’unité azaphosphatrane joue un rôle prépondérant dans la complexation d’anions. / In the wide area of host-guest chemistry, hemicryptophanes, a type of molecular cages combining a cyclotriveratrylene (CTV) unit with another different C3 symmetrical moiety, have received increasing attention. In a first part of this work, the advances in hemicryptophane chemistry have been thoroughly reviewed and the objectives of the thesis have been postulated. Our work mainly concerns the targeted molecular recognition by rational design of hemicryptophanes. Various hemicryptophane structures have been designed as fluorescent sensors for choline phosphate, or for ion-pairs recognition. Original heteroditopic hemicryptophanes bearing tris(2-pyridylmethyl)amine (TPA) units have been synthesized that present a great interest for further applications in molecular recognition. We investigated the stereoselective recognition of carbohydrates using enantiopure hemicryptophanes combining three classes of chirality on seven stereogenic units. At last, we described the breathing motion of a series of enantiopure cages, complementing the rare application of hemicryptophanes as molecular machines.Hemicryptophane vanadium(V) complexes, have been developed as efficient supramolecular catalysts for sulfoxidation and for the catalytic lignin oxidation. Azaphosphatrane-functionalized hemicryptophanes were developed as hydrogen-bonding organocatalysts for the ring-opening polymerization of lactide. Finally, my attention has opened to a more prospective view focusing on cages constructed by self-assembly, and we have demonstrated the feasibility of introducing azaphosphatrane moieties into tetrahedron capsules using subcomponent self-assembly, and also proved for the first time the utility of azaphosphatranes as anion binding moieties.

La préparation de briques élémentaires de pillar[5]arènes « clickables » nous ont permis de construire des édifices moléculaires complexes, en greffant différents groupements fonctionnels autour du coeur macrocyclique. Dans ce contexte, des nouveaux dérivés du pillar[5]arène présentant des propriétés cristaux-liquides ont été synthétisés en greffant du p-dodecyloxybenzoate ou encore des dendrons de type percec. D’autres part, des dérivés pillarèniques portant des unités de porphyrines ont été préparés à partir du squelette « clickable » pillar[5]arène et de porphyrines de Zinc portant des fonctions alcynes vrai. Les études de ce système par RMN du proton à des températures variables ont permis de mettre en évidence un équilibre conformationnel dynamique conduisant au repliement des molécules. Ceci a été expliqué par une complexation intramoléculaire des porphyrines de Zinc par les groupements 1,2,3-triazole. Finalement un support « clickable » detype [2]rotaxane comportant une porphyrine base libre comme bouchon, a été préparé et ensuite fonctionnalisé par dix porphyrines de Zinc permettant l’obtention d’un dispositif supramoléculaire photoactif. / Clickable pillar[5]arene building blocks have been used for the efficient grafting of peripheral subunits onto the macrocyclic core. New liquid-crystalline pillar[5]arene derivatives have been prepared by grafting either p-dodecyloxybenzoate groups or percec-type dendrons on the macrocyclic scaffold. On the other hand, pillar[5]arene derivatives bearing peripheral porphyrin subunits have been efficiently prepared from the clickable pillar[5]arene building block and Zn(II)-porphyrin derivatives bearing a terminal alkyne function. Owing to an intramolecular complexation of the peripheral Zn(II)-porphyrin moieties by 1,2,3-triazole subunits, an original dynamic conformational equilibrium leading to a folding of the molecules has been evidenced by variable temperature 1H NMR studies. Finally, a clickable [2]rotaxane scaffold incorporating a free-base porphyrin stopper has been prepared and functionalized with ten peripheral Zn(II)-porphyrin moieties to afford a sophisticated photoactive supramolecular device.

Uma nova série de metaloporfirinas supermoleculares não-planares foi obtida por meio de automontagem coordenativa de meso tetra(3-piridil)porfirinas e complexos de rutênio polipiridina ([Ru(bipy)2Cl]+ e [Ru(bipy)2(OH2)]2+). Suas propriedades estruturais e eletrônicas foram investigadas por espectroscopia eletrônica, espectrometria de massas, voltametria cíclica e espectroeletroquímica. As influências do acoplamento eletrônico e da mudança da geometria molecular também foram avaliados, tanto no estado gasoso quanto em solução, e os resultados, comparados com a série de isômeros planares obtidos através da coordenação de complexos de rutênio polipiridina as meso tetra(4-piridil)porfirinas. Nanomateriais eletrostaticamente montados, camada por camada, com derivados aniônicos de porfirinas e ftalocianinas foram elaborados. As propriedades eletrocatalíticas dos mesmos foram investigadas, frente a substratos de interesse como nitrito e sulfito. Efeitos supramoleculares conformacionais e eletrônicos foram observados, tanto em solução quanto nos filmes dos nanomateriais porfirínicos supramoleculares. Verificou-se também, uma influência significativa do pH e do íon metálico coordenado à porfirina nos processos de oxidação e de redução de nitrito e de sulfito. / A new series of nonplanar supermolecular metalloporphyrins have been obtained by coordenative self-assembly of meso-tetra(3-pyridyl)porphyrins and ruthenium complexes such as [Ru(bipy)2Cl]+ and [Ru(bipy)2(OH2)]2+. The electronic and structural properties have been investigated by electronic spectroscopy, mass spectrometry, cyclic voltammetry, and spectroelectrochemistry. The effects of the electronic coupling and molecular geometry on the molecular and nanomaterials properties were investigated in the gas phase and in solution. All results were compared with that obtained for the planar isomers obtained by the coordination of four [Ru(bipy)2Cl] groups to the meso-tetra(4-pyridyl)porphyrins. New nanomaterials were obtained by layer-by-layer electrostatic assembly of those supermolecular cationic porphyrins and tetrasulfonated porphyrins or phthalocyanines. The electrocatalytic properties were investigated for nitrite and sulfite. Electronic and supramolecular conformational effects were observed for those species in solution and in films of the nanomaterials. Moreover, a significant effect of the pH and of the transition metal ion coordinated to the porphyrin ring on the electrocatalytic activity were also observed.