Im Hinblick auf eine spätere Anwendung als Katalysatorträger in Hydrierungsreaktionen wurden in dieser Arbeit Adsorptionseigenschaften von Metall-Organischen Gerüstverbindungen (MOFs) in der Flüssigphasenadsorption untersucht. In den Experimenten wurden Materialien gegenübergestellt, bei denen entweder freie Koordinationsstellen am Metallatom (MIL 101, DUT 9, HKUST 1) oder eine abgeschlossene Koordinationssphäre (MOF 5, Zn4O(btb)2, Zn2(bdc)2dabco, ZIF 8, DUT 4, DUT 6) in der Struktur vorlagen. Die Substrate und Lösungsmittel wurden hinsichtlich auf die spätere Verwendung als Edukte in der Hydrierungsreaktion ausgewählt. Neben dem polaren Zimtsäureethylester kamen unpolare Substrate wie Styrol, cis-Cyccloocten und Diphenylacetylen zum Einsatz. Die Materialien wurden desweiteren auf ihre Eignung und Stabilität in der Flüssigphasenhydrierung getestet. Da die untersuchten Metall-Organischen Gerüstverbindungen selbst nicht hydrieraktiv sind, wurden sie als Matrix für die Synthese von Palladium-Nanopartikeln (mittels Incipient Wetness Infiltration) verwendet. Als Referenzkatalysatoren kamen kommerziell erhältliche Pd-Trägerkatalysatoren (Pd@C, Pd@NoritA) und Pd@MOF 5 zum Einsatz. Bei den Experimenten erwies sich Pd@MIL 101 als besonders stabil gegenüber den Reduktions- und Reaktionsbedingungen, sowohl in Gasphasen- als auch Flüssigphasenhydrierungen. Die erzielten Ergebnisse zeigen den starken Einfluss des spezifischen Porenvolumens, der Form der Pore bzw. des Poreneingangs, der Polarität des Substrates und des verwendeten Lösungsmittels auf die adsorbierte Substratmenge. Sie verdeutlichen die Relevanz von Adsorptionsuntersuchungen an neuen Materialien. Das Verständnis der Wechselwirkungen zwischen den verwendeten Lösungsmitteln, Substraten und Adsorbentien ist ein entscheidender Faktor bei der Optimierung von Adsorptionsprozessen und bei der Verwendung von MOFs in heterogen katalysierten Reaktionen. Diese Arbeit zeigt das hohe Potential von Metall-Organischen Materialien im Bereich der heterogenen Katalyse. Unter Verwendung dieser Verbindungen als Trägermaterialien für Palladium können sehr hohe Aktivitäten in Hydrierungsreaktionen erreicht werden, welche z.T. auch industriell genutzte, Aktivkohle basierte Pd-Trägerkatalysatoren übertreffen.

abstract: Amine-modified solid sorbents and membrane separation are promising technologies for separation and capture of carbon dioxide (CO2) from combustion flue gas. Amine absorption processes are mature, but still have room for improvement. This work focused on the synthesis of amine-modified aerogels and metal-organic framework-5 (MOF-5) membranes for CO2 separation. A series of solid sorbents were synthesized by functionalizing amines on the surface of silica aerogels. This was done by three coating methods: physical adsorption, magnetically assisted impact coating (MAIC) and atomic layer deposition (ALD). CO2 adsorption capacity of the sorbents was measured at room temperature in a Cahn microbalance. The sorbents synthesized by physical adsorption show the largest CO2 adsorption capacity (1.43-1.63 mmol CO2/g). An additional sorbent synthesized by ALD on hydrophilic aerogels at atmospheric pressures shows an adsorption capacity of 1.23 mmol CO2/g. Studies on one amine-modified sorbent show that the powder is of agglomerate bubbling fluidization (ABF) type. The powder is difficult to fluidize and has limited bed expansion. The ultimate goal is to configure the amine-modified sorbents in a micro-jet assisted gas fluidized bed to conduct adsorption studies. MOF-5 membranes were synthesized on α-alumina supports by two methods: in situ synthesis and secondary growth synthesis. Characterization by scanning electron microscope (SEM) imaging and X-ray diffraction (XRD) show that the membranes prepared by both methods have a thickness of 14-16 μm, and a MOF-5 crystal size of 15-25 μm with no apparent orientation. Single gas permeation results indicate that the gas transport through both membranes is determined by a combination of Knudsen diffusion and viscous flow. The contribution of viscous flow indicates that the membranes have defects. / Dissertation/Thesis / M.S. Chemical Engineering 2010

This thesis is largely a study of the ADOR process (assembly-disassembly-organisation-reassembly) when applied to zeolite UTL. The final chapter of this thesis deals with the adsorption of the medical gases NO and CO onto the metal organic framework NiNaSIP. Chapter 4 is devoted to the disassembly and organisation steps of the ADOR process. Calcined UTL was hydrolysed using 0.1 – 12 M HCl solutions from 75 – 95 °C run over 10 mins to 72 hrs. A three step mechanism is proposed, which is comprised of an initial rapid hydrolysis that removes the majority of the interlayer constituents of UTL, causing the silica-rich layers to largely collapse. This is followed by a slow, temperature and molarity dependent, deintercalation process that sees the remainder of the interlayer material removed resulting in the full collapse of the layers to form IPC-1P. The third step is a temperature and molarity dependent rebuilding process, whereby the interlayer region is slowly rebuilt, eventually forming a precursor which upon calcination becomes IPC-2 (OKO). Chapter 5 uses the pair distribution function (PDF) technique to structurally confirm the intermediate of the ADORable zeolite UTL. The intermediate, IPC-1P, is a disordered layered compound formed by the hydrolysis of UTL in 0.1 M HCl. Its structure is unsolvable by traditional X-ray diffraction techniques. The PDF technique was first benchmarked against high-quality synchrotron Rietveld refinements of IPC-2 (OKO) and IPC-4 (PCR) – two end products of IPC-1P condensation that share very similar structural features. An IPC-1P starting model derived from density functional theory was used for the PDF refinement, which yielded a final fit of Rw = 18% and a geometrically reasonable structure. This confirms that the layers do stay intact throughout the ADOR process, and shows that PDF is a viable technique for layered zeolite structure determination. Chapter 6 examines the reassembly stage by following the in-situ calcination of a variety of hydrolysed intermediates into their three-dimensional counterparts. Beamline I11 at Diamond Light Source provided high-quality PXRD patterns as a function of temperature, which were refined against using sequential Pawley refinements to track the unit cell changes. 0.1, 1.75, 2.5 and 12 M hydrolysed lamellar precursor phases were calcined. The largest unit cell changes were observed for 0.1 M, and the smallest for 12 M. This shows that increasing the molarity must prebuild most of the interlayer connections, such that upon calcination, only minimal condensation occurs to fully connect the layers. Chapter 7 probes the uptake of the medical gases CO and NO into the metal organic framework NiNaSIP. An in-situ single-crystal XRD study was undertaken using an environmental gas cell at beamline 11.3.1 at the Advanced Light Source. NiNaSIP was first dehydrated to reveal an open nickel site, which acted as the main site of adsorption for the inputted gases. NO was observed in a bent geometry at an occupancy of 40 % and a Ni – N bond length of 2.166(16) Å. The oxygen was modelled to be disordered over two sites. CO was not fully observed, as only the carbon was able to be modelled with an occupancy of 31.2 % and a Ni – C bond length of 2.27(3) Å.

La synthèse et la caractérisation de nouveaux matériaux sont des enjeux majeurs en chimie et en physique. En particulier, les réseaux organométalliques (metal –oganic frameworks : MOFs) avec deux ou plusieurs fonctionnalités couplées, encore rares, sont très attractifs en raison de leur grande variété de propriétés et de leurs applications prometteuses connectant de nombreuses disciplines.Le développement de nouveaux matériaux fascinants peut avoir un impact considérable sur notre vie quotidienne, ce qui explique en partie l'intensification de la recherche dans le cadre de la science des matériaux et de la matière condensée.Cette thèse se concentre sur la synthèse et la caractérisation des propriétés physiques de structures magnétiques basées sur le formiate de métal en utilisant la combinaison de diffraction par neutrons et par rayons X ainsi que d'autres techniques.Les réseaux de métal-formiate sont un sous-groupe spécifique des réseaux organométalliques, typiquement synthétisés en faisant réagir un ligand organique avec un sel métallique sous des conditions solvo-thermiques ou par des techniques d'évaporation ou de diffusion lente. Les centres métalliques sont liés par des molécules de formiate formant un cadre anionique qui peut être équilibré électrochimiquement par des amines protonées.Dans ce travail, j’ai étudié la structure cristalline, les transitions de phases et les propriétés magnétiques de deux familles de composés qui sont représentés par les composés hétéro-métalliques ou à valence mixtes, adoptant une structure de type niccolite et des composés homo-métalliques adoptant une structure pérovskite (ABX3). Les composés suivants ont été synthétisés et caractérisés: [(CH3)2NH3][FeIIIMII(HCOO)6] (M = Mg, Mn, Fe, Co, Ni), [(CH3)2NH3][FeIIIFeII(HCOO)6], [(CH3NH3)[M(HCOO)3] (M = Co, Mn, Fe, Ni, Cu), and [(NH4)[Mn(HCOO)3].Le choix d'utiliser des ions métalliques spécifiques a été motivé par leur configuration électronique différente et, par conséquent, par les différents comportements physiques, c'est-à-dire une grande différence bien connue dans l'anisotropie magnétique des différents ions divalents utilisés dans cette étude. Outre les effets sur les propriétés lorsque différents ions métalliques divalents sont introduits dans la structure, un autre aspect intéressant est l’effet produit en changeant la nature des contre-ions. Même s'il n'y a pas de corrélation claire entre le contre-ion sélectionné et le changement de comportement magnétique, la diffraction des neutrons permet d'élucider les différences dans la structure nucléaire et dans la structure magnétique lorsque différents contre-ions sont utilisés. Par ailleurs, ce travail, nous aide à comparer nos résultats neutroniques avec les mesures complémentaires de magnétométrie. Une variété de phénomènes magnétiques tels que le comportement ferromagnétique, l'ordre antiferromagnétique, l’angle de basculement spin ont été observés dans les composés étudiés. De plus, du point de vue de la structure nucléaire, différentes transitions de phases ont été détectées impliquant par exemple l'ordre-désordre du contre-ion employé (dans [(CH3)2NH3][FeIIIMII(HCOO)6] par exemple), ou le passage d'une phase commensureable à une phase incommensurable donnant lieu à une modulation de la structure (dans [(CH3NH3)[Co(HCOO)3] par exemple). / The synthesis and the characterization of new materials are key challenges in chemistry and physics. In particular, metal–organic frameworks (MOFs) with two or more coupled functionalities are still rare and very attractive candidates because of their wide variety of properties, and promising applications interesting many disciplines. The impact of the development of new fascinating materials on our day life might be considerable. This is also one of the reason explaining the intense increasing of the research in material science and condensed matter.This thesis is focused on the synthesis and the physical characterization of magnetic metal formate frameworks using the combination of neutron and synchrotron X-Ray diffraction as well as other techniques. Metal-formate frameworks are a specific subgroup of metal-organic frameworks, where the metal centres are linked by the formate molecules to form an anionic framework. The negative charge of the framework is balanced by a counter-cation inside the frameworks’ cavities, that can be for example protonated amines.Typically, these compounds are synthesized by reacting formate or formic acid with a metal salt under solvo-thermal conditions or by slow evaporation or diffusion techniques.In this work, I investigated the crystal structure, phase transitions and magnetic properties of two families of metal formate frameworks, which are represented by the hetero-metallic or mixed valance compounds adopting a niccolite-like structure, and the homo-metallic compounds adopting a perovskite-like (ABX3) structure.Altogether, the following compounds were synthesized and characterized: [(CH3)2NH3][FeIIIMII(HCOO)6] (M = Mg, Mn, Fe, Co, Ni), [(CH3)2NH3][FeIIIFeII(HCOO)6], [(CH3NH3)[M(HCOO)3] (M = Co, Mn, Fe, Ni, Cu), and [(NH4)[Mn(HCOO)3].The choice of using specific metal ions has been motivated by their different electronic configuration and therefore different physical behaviours, i.e. a large difference in the magnetic anisotropy is well known among the different divalent ions used in this study. Beside the effects on the properties when different divalent metal ions were introduced within the framework, the effects of the nature of the counterions was investigated.Even though there is not a clear correlation between the selected counterion and the change of magnetic behaviour, neutron diffraction allows elucidating the differences in the nuclear and in the magnetic structure when different counterions are used. Moreover, these works help us to compare our neutron results with the magnetometry measurements, which is a complementary technique.A variety of magnetic phenomena such as ferromagnetic behaviour, antiferromagnetic ordering, spin canting have been observed in the compounds studied. Furthermore, from the nuclear structure point of view many different kind of phase transitions were detected involving for instance, the order-disorder of the counter ion employed (in [(CH3)2NH3][FeIIIMII(HCOO)6] for example), or the transition from a commensurate to incommensurate phase giving rise to a modulation of the structure (in [(CH3NH3)[Co(HCOO)3] for example).

La pollution de l'environnement, sa remédiation et l'obtention de sources d'énergie plus propres et plus efficaces sont des problématiques difficiles auxquels les humains sont confrontés. Parmi les nombreux matériaux développés par les scientifiques, les polymères de coordination cristallins type MOFs sont de plus en plus développés dans plusieurs domaines, du fait de la facilité et la versatilité de leur synthèse. La recherche sur ces matériaux est récente, mais les possibilités qu’offrent ces matériaux pour différentes applications sont énormes.C'est dans ce cadre que nous avons travaillé sur la conception et la synthèse de différents MOF pour la récupération, le recyclage et/ou la dégradation de certains polluants. En utilisant différentes approches de synthèse, nous avons obtenu des matériaux efficaces pour les diffèrent applications ciblées de ces matériaux. Nous pensons que les MOF ont le potentiel pour solutionner certains problèmes cruciaux comme la décontamination de l'environnement. / The pollution of the environment, its remediation and to obtain a cleaner and more efficient energy sources are some of the most challenging topics that humans are now facing. Among the several materials that scientists have developed, Metal Organic Frameworks (MOFs) are gaining a lot of attention on several fields due to the easiness and the versatility in which these materials can be designed, synthesized and used. Even when research on these materials is still young, the possibilities that they offer are enormous.It is on this frame that our work group has worked on the design and the synthesis of different MOFs for the recovery, the recycling and/or the degradation of some pollutants of interest. By using different synthesis approaches we have tested the versatility in the synthesis and the possible applications of these materials. We believe that MOFs hold the potential to solve some crucial issues in the recovery of the environment.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Hybrid coordination networks such as metal-organic networks, also known as MOF (Metal Organic Framework), have attracted great attention from the scientific community due to their wide diversity and wide range of applications, however, the investigation of applications of these structures still forms a large area of research, with great exploration potential, either through experimental or theoretical chemistry. The present work aims at the use of computational chemistry methods with focus on semiempirical methods for the study of MOFs, so we will initially address results regarding the evaluation of the prediction capacity of solid phase structures of MOFs containing lanthanide as a metallic center. Performed using the semi-empirical methods Sparkle/AM1, Sparkle/PM3, Sparkle/PM6, Sparkle/PM7, Sparkle/RM1 and RM1. The results obtained from the calculation of optimization of the structures suggest that the Sparkle/PM3 and Sparkle/RM1 methods provide more accurate results, with less variability and great agreement with the experimental data, both structural and luminescent. The health application study initially evaluated the structure of the drug doxorubicin and MOF ZnDBC ([Zn(BDC)(H2O)2]n), and then evaluated the drug’s anchoring potential, in order to obtain results that justify the MOF to be chosen as a candidate for application as a drug carrier. This analysis resulted in obtaining a viable anchorage between the MOF lamellae. A simulation of the effects of temperature variation on the structure of the MOF EuBTC ([Eu2(MELL)(H2O)6]) and its effect on the luminescent properties was performed to obtain data that could validate your application with gunshot residues marker, aiming at its use in public safety. This analysis explored the potential of structural description of Sparkle/PM3 as well as the obtaining of luminescent properties, which led to the conclusion that the increase in temperature resulted in an increase in the emission quantum yield caused by the loss of water molecules contained in the first sphere of the coordinating polyhedron. For the application of MOFs in energy, an investigation was carried out regarding the degree of adsorption of the hydrogen gas and methane in the IRMOF-8 and in this one after the doping of its aromatic rings with aluminum atoms, in order to elucidate the effect that the realization of this Doping brings the storage capacity of these gases, for use in gas storage cylinders used in motor vehicles. And it was verified a slight reduction in the storage capacity of the methane gas, since for the hydrogen gas no significant changes were verified. Finally, a study was carried out to evaluate the capture capacity of carbon dioxide and hydrogen sulfide gases in IRMOF-8 and in this doped with aluminum, so the same structure of the previous study was used. It was found that doping gave a considerable increase in the degree of adsorption, being more effective for the carbon dioxide, whose interactions had energy of magnitude of a chemical adsorption. / As redes metalorgânicas também conhecidas como MOF (do inglês Metal Organic Framework) têm atraído grande atenção da comunidade científica devido a sua ampla diversidade e vasta gama de aplicações. Entretanto, a investigação de aplicações destas estruturas ainda configura uma grande área de pesquisa, com potencial de exploração, seja por meio de um viés experimental ou teórico. O presente trabalho tem como objetivo o uso de métodos de química computacional com foco em métodos semiempíricos para o estudo das MOFs. Assim, inicialmente abordaremos resultados referentes à avaliação da capacidade de predição das estruturas em fase sólida de MOFs contendo íons lantanídeos como centro metálico. Este estudo foi realizado através do uso dos métodos semiempíricos Sparkle/AM1, Sparkle/PM3, Sparkle/PM6, Sparkle/PM7, Sparkle/RM1 e o RM1. Os resultados obtidos a partir do cálculo de otimização das estruturas sugerem que o método Sparkle/PM3 e o Sparkle/RM1 proporcionam resultados mais exatos, com menor variabilidade e grande concordância com os dados experimentais, tanto estruturais como luminescentes. Foi avaliado o potencial de ancoragem da doxorrubicina na MOF ZnDBC ([Zn(BDC)(H2O)2]n). Esta análise mostrou viabilidade de ancoragem entre as lamelas da MOF. Além disso, foi realizada uma simulação dos efeitos da variação da temperatura sobre as propriedades luminescentes da MOF EuBTC ([Eu2(MELL)(H2O)6). Com isso, buscou-se validar a aplicação desta MOF como marcador de resíduos de disparo de arma de fogo. Esta análise explorou o potencial de descrição estrutural do Sparkle/PM3, bem como obtenção de propriedades luminescentes. A elevação da temperatura resultou no aumento do rendimento quântico de emissão, causado pela perda de moléculas de água contidas na primeira esfera do poliedro de coordenação. Para aplicação de MOFs na área de energia, foi realizada uma investigação referente ao grau de adsorção de gás hidrogênio e metano na IRMOF-8. Foi realizada a inclusão de átomos de alumínio nos anéis aromáticos, visando elucidar qual o efeito provocado sobre a capacidade de armazenamento desses gases. A dopagem levou a uma leve redução na capacidade de armazenamento do gás metano. Já para o gás hidrogênio não foram verificadas alterações significativas. Por fim, foi feito um estudo de avaliação da capacidade de captura dos gases dióxido de carbono e sulfeto de hidrogênio na IRMOF-8, tanto pura quanto dopada com alumínio. Notou-se que a dopagem proporcionou um considerável aumento no grau de adsorção, sendo mais efetivo para o dióxido de carbono, cujas interações tiveram energia de magnitude de uma adsorção química. / São Cristóvão, SE

Nous avons déterminé l'alignement des niveaux énergétiques d’un solide moléculaire organique, transporteurs de trous, avec un oxyde d'indium dopé à l’étain (ITO), un conducteur transparent. Les molécules étudiées, basées sur une structure dipyranylidène (DIP), diffèrent par leur hétéroatome (O, S et Se). La spectroscopie de photoémission X a été utilisée pour déterminer cet alignement, et nous avons étudié l'orientation moléculaire par spectromicroscopie d'absorption X. Des calculs DFT ont été réalisés pour interpréter les données spectroscopiques. Nous avons constaté la présence d'un transfert de charge, au moins pour les dérivés oxygénés et soufrés. Celui-ci a lieu des molécules vers l’ITO, lorsqu'ils sont en contact intime avec le substrat. Nous avons déterminé la barrière d'injection des trous entre le niveau de Fermi de l’ITO et la HOMO du solide organique. Notre approche expérimentale met l'accent sur la relation entre les propriétés structurelles et les propriétés électroniques. Ces résultats ont été obtenus pendant des runs synchroton en France (SOLEIL), en Italie (ELETTRA) et en Suisse (SLS). / The energy level alignment of hole-transport organic molecular solids with indium tin oxide (ITO), a transparent conducting oxide, has been characterized. The studied molecules, based on the dipyranylidene (DIP) structure, differ by the heteroatom (O, S and Se). Synchrotron photoemission electron spectroscopy has been used to determine the alignment, and we investigated the molecular orientation via X-ray absorption spectromicroscopy. By interpreting spectroscopic data in the light of DFT calculations, we found evidence of the presence of charge transfer from the molecules to the ITO, when they are in intimate contact with the substrate, at least for the O and S-DIPs. The hole injection barrier between the ITO Fermi level and the organic HOMO was obtained. Our experimental approach emphasizes the relationship between structural and electronic properties. These results were obtained during beamtimes in France (SOLEIL), Italy (ELETTRA) and Switzerland (SLS).

No description available.

Les réseaux de coordination, ou Metal Organic Frameworks (MOFs), sont des architectures cristallines hybrides organiques-inorganiques qui présentent des propriétés découlant de leurs compostions et de leurs architectures. L'objectif de ce travail fut la synthèse contrôlée de nouveaux réseaux de coordination homo- (MOFs) et hétérométalliques (M'MOFs) à base de ligands dipyrrines (dpms). Dans une première partie, une stratégie de synthèse basée sur l'auto-assemblage a permis l'obtention d'une nouvelle famille de réseaux constituée de MOFs luminescents [CdII(dpm)2] et de MOFs [NiII(dpm)2]. Dans une seconde partie, l'utilisation d'une stratégie séquentielle a permis de préparer des M'MOFs de type grille basés sur différents cations métalliques primaires (CuII, PdII, ZnII) et différents nœuds métalliques secondaires (CdCl2, Cd(NCS)2, Fe(NCS)2). Ces M'MOFs font partie des rares exemples d’architectures modulables conçues par une approche rationnelle et prédictible. De plus, il a été montré que ces composés pouvaient être synthétisés en une seule étape par une méthode avantageuse de synthèse "one pot". Pour finir, une stratégie "zip-Unzip-Rezip" consistant à convertir des MOFs préalablement formés en M'MOFs hétérométalliques par l'emploi de ligands auxiliaires a été mise au point. Cette nouvelle voie permet d'incorporer aisément de la fonctionnalité dans des architectures. / Coordination networks or Metal Organic Frameworks (MOFs) are hybrid organic-Inorganic crystalline architectures displaying properties resulting from their composition and organization. The aim of this work was to synthesize, in a controlled manner, dipyrrin based new homometallic (MOFs) and heterometallic (M'MOF) coordination networks.In the first part, a strategy based on self-Assembly leading to the formation of a new family of luminescent networks [CdII(dpm)2] MOFs and [NiII(dpm)2] MOFs is described.In a second part, generation of grid-Type M'MOFs based on different primary cations (CuII, PdII, ZnII) and secondary metallic nodes (CdCl2, Cd(NCS)2, Fe(NCS)2) by a sequential strategy is presented and discussed. These M'MOFs are among the rare examples of predesigned architectures displaying substantial modularity. Importantly, it has been also demonstrated that these architectures may be efficiently prepared by a "one pot" procedure. Finally, a "zip-Unzip-Rezip" strategy consisting in the conversion of preformed MOFs into M'MOFs using auxillary ligands was developed. This unprecedented approach allows the introduction of functionality within the architectures.

L'objectif de cette thèse est la synthèse, la caractérisation et l'étude de complexes métalliquesluminescents, en particulier de Pt (II), leurs propriétés d'agrégation en solution, mais également dansun espace confiné ainsi qu’en surface. L'incorporation de complexes de métaux de transition dans lastructure poreuse, et ainsi que leur dépôt à la surface de nanoparticules et dans un cadre métalloorganique(MOF), par greffage post-synthétique, ont été étudiés. Sont également étudiés lacorrélation entre les propriétés de films d’une série de complexes de Pt(II) avec leur morphologie,leur mobilité électronique et la simulation de leur structure auto-assemblée par diffraction auxrayons-X. Les propriétés de luminescence de complexes amphiphiles de Pt(II) sont améliorées àl’intérieur de nanoparticules de silice mesoporeuse par la création d’un d’espace confiné. Un effetsimilaire est observé par le dépôt de complexes de Pt(II) fonctionnalisés sur une surface denanoparticules d’or. La luminescence d’un cadre organométallique a été modifiée par greffage postsynthétiquede complexes d’Ir(III) et de Pt(II). / The aim of this thesis is the synthesis, characterization and investigation of luminescent metalcomplexes, and in particular of Pt(II) compounds, their aggregation properties in solution but inconfined space as well. The incorporation of transition metal complexes in porous structure, and inparticular in a metal-organic framework (MOF), by post-synthesis grafting, have been investigated.Luminescence properties of amphiphilic Pt(II) complexes were enhanced inside mesoporous silicananoparticles by the creation of a confined space. Similar effect is observed by deposition offunctionalized Pt(II) complexes on gold nanoparticles surface. Luminescence of metal organicframework was tuned by post-synthetic grafting of Ir(III) and Pt(II) complexes.