La formation de polymères de coordination poreux et chiraux ainsi que leur utilisation pour des processus énantiosélectifs est actuellement un des domaines de grand intérêt en chimie. La formation de ces matériaux est rendue possible par le biais des concepts développés dans le domaine de la tectonique moléculaire. Les travaux présentés dans cette thèse s’inscriventdirectement dans cette thématique. Les synthèses de tectons organiques chiraux sont présentées. Leur combinaison avec divers centres métalliques, via différentes méthodes de cristallisation, a permis l’obtention de monocristaux qui ont été étudiés par diffraction des rayons X sur monocristal. Dans un premier temps, des polymères de coordination homochiraux, obtenus par l’utilisation de tectons dotés de sites coordinants neutres sont présentés. Des réseaux de type cuboïde présentant des canaux monodimensionnels au sein de leur architecture sont notamment décrits. Par la suite, des édifices mono- et bi-dimensionnels de géométries diverses sont discutés. Pour certains de ces cristaux, des interactions de plus faible énergie que la liaison de coordination permettent la formation de réseaux moléculaires de plus haute dimensionnalité. Enfin, dans une dernière partie, l’utilisation de tectons dotés de sites coordinants chargés est discutée. Des réseaux tridimensionnels homochiraux poreux et robustes sont décrits. Ces derniers sont des candidats de choix pour des procédés énantiosélectifs de séparation. Leur propension à encapsuler des gaz (N2 et CO2) est présentée. / The synthesis and the use of porous chiral coordination polymers for enantioselective processes are of current interest and prime importance in chemistry. These crystalline materials are mainly obtained by combinations of well-designed organic tectons and properly chosen metallic components. This thesis deals with the synthesis of organic chiral building blocks and their combinations with a variety of metallic salts leading to chiral coordination networks. In a first part, the use of tectons bearing neutral coordinating sites is described. Homochiral cuboid architectures displaying monodimensional channels are presented. In the second part, mono- and bi-dimensional networks of various geometries are described. In some cases, within crystals, interactions lower in energy than the coordination bond are observed and are responsible for the formation of molecular networks of higher dimensionality. Finally, the use of organic tectons displaying charged interaction sites is presented. Their combination with metallatectons under thermal treatments affords robust tridimensional homochiralarchitectures displaying cavities. These materials are interesting candidates for enantioselective recognition and separation. Their gas adsorption propensity (N2 and CO2) is briefly discussed.

Les bisoxazolines de symétrie C2, ligands chiraux bidentates formés par deux cycles oxazolines séparés par un atome de carbone portant deux substituants identiques, font partie de ligands le plus utilisés en chimie de coordination et en catalyse asymétrique (homogène et hétérogène). Ce travail décrit la synthèse de treize ligands polytopiques chiraux comportant des unités bisoxazolines. Ces ligands ont été par la suite utilisés, d'une part, en tant que ligands chiraux pour la construction des catalyseurs auto-supportés de Cu(II)/ ligand polytopique (catalyseurs testés par la suite dans les réactions d' α-amination de β-cétoesters énantiosélective, de desymétrisation asymétrique par benzoylation de meso-diols, de dédoublement cinétique de rac-diols et dans la nitroaldolisation du nitrobenzaldehyde ou réaction de Henry); et d'autre part, en tant que briques deconstruction dans l'autoassemblage alterné et contrôlé de polymères de coordination métalloorganiques racémiques et énantiopurs. / Chiral C2-symmetric bis(oxazolines), bidentate ligands formed by two oxazoline rings separated by a carbon atom with two identical substituents, are one of the most popular types of chiral ligands which have already been successfully used in coordination chemistry and asymmetric catalysis (heterogeneous and homogeneous). This work describes the synthesis of thirteen polytopic chiral ligands bearing bis(oxazolines) moieties which have then been used, on the one hand, as chiral ligands for the construction of selfsupported Cu(II)/ polytopic ligand catalysts which were subsequently tested in the enantioselective α-hydrazination of β-ketoesters, the asymmetric desymmetrization of meso-diols by benzoylation and the kinetic resolution of rac-diols and the nitroaldolisation reaction (Henry reaction); and on the other hand, as organic building blocks for the controlled and alternate self-assembly of racemic and enantiopur metal-organic coordination polymers.

Nature has always remained a constant source of inspiration for chemists for synthesizing natural products, mimicking enzymatic reactions or to construct molecular architectures resembling biological assemblies. With the rapid growth of ‘Supramolecular Chemistry’ along with the advancement of the synthetic methodologies, molecular systems with brand new complexities have been synthesized, alongside the efficacy of weak, reversible non-covalent interactions have also been extensively explored. A number of such forces including hydrogen bonding, solvophobic effect, dynamic covalent interactions and metal-ligand coordination have been exploited to assemble the molecular building blocks and stitch them together to construct discrete ‘self-assembled’ architectures integrated with desired functionalities. Metal-ligand coordination driven self-assembly certainly evolved as one of the most successful approaches for the construction of discrete supramolecular architectures during last two and half decades. The high directionality and reversible nature of certain metal-ligand bonds allow the pre-designing of sophisticated architectures which can be successfully obtained by ‘error corrections’ via a thermodynamically controlled self-assembly process. Numerous aesthetically elegant two dimensional (2D) and three dimensional (3D) metallosupramolecular architectures have been constructed which have been studied for various potential applications including guest encapsulation, catalysis, sensing, optoelectronics, drug delivery, protection of reactive species etc. Construction of such molecular architectures uses symmetric and rigid building blocks which strictly preserves their geometrical coding and thus finally determines the fate of the self-assembly. Pyridyl-based donors have been extensively used due to their well-behaved coordination with transition metal ions. Interestingly, imidazole based donors remained almost unexplored for such purpose mainly due to the rotational flexibility of imidazole moieties owing to the lack of -electron delocalization with the aromatic backbone, which makes pre-designing an architecture extremely difficult. However, this unpredictability can lead to the formation of unprecedented molecular architectures. Furthermore, the conventional rigid ‘acceptors’ used in the ‘directional bonding approach’ always results in the formation of rigid assemblies, which cannot be utilized for the construction of smart molecular machine based applications. In this context, incorporation of restricted rigidity in the building blocks can be a convenient approach to construct versatile and flexible supramolecular architectures. Although flexible donors are quite common in coordination-driven self-assembly, the use of flexible metal acceptor is scarcely Highly symmetric spherical assemblies of square planer Pd(II) and Pt(II) ions are one of the most extensively studied metallosupramolecular architectures owing to their topological similarity with the spherical virus capsids. Unfortunately, none of the reported molecular spheres are soluble in water which restricts their applications in aqueous media. On the other hand, most of the metallosupramolecular architectures cannot be used for redox based applications as the oxidation state of the associated metal ions must be kept unaltered. Although, assemblies constructed mainly by the ferrocene containing acceptors are shown to be exhibiting redox property, the donor inherited redox active metallosupramolecular systems are extremely rare. Discrete 3D metallosupramolecular cages have been extensively studied as synthetic hosts where the hydrophobic pockets have been utilized as safe shelter for reactive species, for catalyzing chemical transformations, tuning electronic and optical properties of guest molecules, as delivery vehicle for drug molecules etc. However, a major drawback of many such 3D cages is associated with their closed-shell topology, where the large cavities are accessible though relatively much smaller apertures which prevent larger guest molecules to enter inside. So, an interesting finding in this field would be to construct molecular hosts with larger apertures. Picric acid (PA) is a strong organic acid and like many other polynitroaromatic compounds, it is a powerful explosive. In addition, it has large scale industrial application for the synthesis of dyes and pharmaceuticals. However, PA has potential health hazards and it is a water pollutant owing to its high aqueous solubility. Thus, the development of selective receptors which can efficiently interact with PA and detect it at very lower concentration is an appealing field of research. Chapter 1 briefly discusses the history of supramolecular chemistry and the concept of ‘self-assembly’ along with the several synthetic methodologies for the construction of discrete supramolecular architectures. It also includes a brief discussion on the various design approaches to construct 2D and 3D molecular architectures by metal-ligand coordination which is followed by an account on some of the important applications of such metallosupramolecular architectures. At the end, a small introduction on the fluorescence-based detection techniques for PA has also been included. Chapter 2A accounts for the exploration of two linearly substituted benzene bisimidazole donors L1 and L2 for coordination-driven self-assembly. L1 and L2 possesses different ‘natural’ donor angles as the imidazole moieties in L2 are twisted heavily with respect to the phenyl plane due to the steric hindrance exerted by the methyl groups. Interestingly, while the self-assembly of L1 with [cis-(tmeda)Pd(NO3)2] (tmeda = N,N,Nꞌ,Nꞌ-tetramethylethane-1,2-diamine) exclusively formed a [3+3] molecular triangle, the self-assembly of L2 yielded a [4+4] molecular square as the major product with the same acceptor. In addition, similar treatment with the analogous Pt(II) acceptor resulted mixtures of [3+3] and [4+4] assemblies in both cases; however, the [3+3] assembly was the major product in case of L2. These contradictory product distributions in case of L2 with analogous Pd(II) and Pt(II) acceptors could be corroborated by the delicate balance between the entropic and enthalpic contributions. Scheme 1. Self-assembly of L1/L2 with [cis-(tmeda)Pd(NO3)2] and [cis-(tmeda)Pt(NO3)2], respectively. Furthermore, the reactions of L1 and L2 with a 0º bisplatinum acceptor, viz. AntPt yielded the expected [2+2] macrocycles (8 and 9), respectively. However, the interesting observations Scheme 2. Self-assemblies of L1 and L2 with the 0º bisplatinum acceptor AntPt. obtained from the variable temperature NMR studies suggested the existence of a mixture of inter-convertible conformational isomeric structures of 9. Chapter 2B describes the synthesis of a novel semi-rigid bisplatinum acceptor bisPt-NO3 based on benzil backbone for the construction of flexible metallamacrocycles. The benzil group was selected due to its unique rotational flexibility along the benzyl C-C bond which can generate a wide range of bite angles to make it compatible with the variety of donors of diverse shapes and sizes. The acceptor was successfully self-assembled with four different bisimidazole donors (L1-L4) to yield corresponding [2+2] metallamacrocycles (M1-M4) which were characterized by multinuclear NMR and ESI-MS spectrometry; and their structures were elucidated by semi-empirical geometry optimizations. Scheme 3. Self-assembly of [2+2] metallamacrocycles M1-M4 by a semi-rigid bisplatinum acceptor bisPt-NO3. Chapter 3 discusses the synthesis of the very first example of a water soluble molecular sphere MC-1 by the self-assembly of square planar Pd(II) ions with a flexible cationic tritopic donor La(NO3)3 containing 4,4-bispyridyl arms. The structural flexibility of La(NO3)3 makes it capable of binding with metal ions in its syn- or anti-conformations which was also experimentally observed in the structures of the three newly synthesized coordination polymers, viz. Ag-CP, Zn-CP and Cd-CP constructed by using La(NO3)3 as (co)ligand. Finally, the 4:3 self-assembly of [La(NO3)3] and Pd(NO3)2 in aqueous media produced the desired M6L8 type Scheme 4. Self-assembly of the water soluble molecular dice MC-1 from the tricationic tritopic donor La(NO3)3. molecular sphere- MC-1, which contain 36+ overall charges. The compound could be easily solubilized in water after isolation as solid by simple stirring at room temperature. Single crystal X-ray diffraction analysis (SCXRD) revealed the ‘dice’-shaped architecture of MC-1 where the eight faces are occupied by the coordinated Pd2+ ions and the bispyridyl arms and the vertices are occupied by mesityl moieties. MC-1 is stable in aqueous media, however disintegrates in DMSO, as observed by variable temperature NMR experiments. In addition, MC-1 also produced ligand inherited redox signals in cyclic voltammetry experiments. Chapter 4 describes the synthesis of a novel non-symmetric tetraimidazole donor L based on carbazole backbone. The complexity of the donor is associated with the allowed free rotation of the imidazole moieties along with the non-symmetric nature of the carbazole backbone which make L a very unusual donor for coordination-driven self-assembly. The crystal structure of L showed that the presence of the N-Me group caused a greater twisting of the nearby imidazole moieties with respect to the other set of imidazole moieties. The self-assembly of L with [cis-(en)Pd(NO3)2] (en = ethane-1,2-diamine) yielded a mixture of M4L8 and M6L12 type self-assembled products, as evidenced from the ESI-MS spectrometry. However, the DOSY NMR spectra of the product showed a single diffusion coefficient for all the peaks, indicating that both type of assemblies have similar size and hence suggested the formation of a tetrafacial barrel and a cubic architecture. A similar self-assembly of L with [cis-(tmeda)Pd(NO3)2] also produced a water soluble product. ESI-MS spectra in this case only confirmed the formation of a M4L8 assembly- MB-1. SCXRD analysis of the coronene encapsulated complex of MB-1 gave more insights on the sophisticated non-symmetric tetrafacial barrel architecture of MB-1 with large Scheme 5. Construction of the water soluble molecular barrel MB-1 by the self-assembly of a non-symmetric tetraimidazole donor L. rectangular apertures. The centrosymmetric molecule can encapsulate two aromatic guest molecules inside its hydrophobic cavity and was found to be efficiently encapsulating polyaromatic hydrocarbons (PAHs) in aqueous media. In addition, MB-1 has been successfully exploited to carry water insoluble perylene molecule inside HeLa cells for fluorescence imaging purpose without showing significant toxicity. L also formed a water insoluble tetrafacial barrel (MB-2) by self-assembly with [cis-(dppf)Pd(OTf)] (dppf=diphenylphosphino ferrocene) which interestingly has a symmetrical architecture, as evidenced from the SCXRD analysis. The formation of the symmetrical barrel is driven by the steric hindrance between the bulky phenyl groups of the nearby dppf moieties. Chapter 5 reports the study of interactions between picric acid (PA) with a few newly synthesized fluorescent imidazolium salts (S1-S3). The fluorescence titration study of the positively charged receptors with PA showed rapid decrease of the corresponding fluorescence intensities upon gradual addition of PA. The Stern-Volmer plots suggested the involvement of both static and dynamic quenching mechanisms which was further supported by fluorescence lifetime measurements, NMR and UV-Vis spectroscopic analyses. The values of the Stern-Volmer constants (Ksv) reflected strong receptor-PA binding. The quenching efficiency calculations in the presence of several other analytes proved that the receptors are highly selective for PA in both aqueous and non-aqueous media. The mode of interactions in solid state was investigated by the crystal structure analysis of the [S1PA] complex. 1H NMR spectra of the same complex indicated strong interaction between the imidazolium moieties of the receptor Scheme 6. The fluorescent imidazolium salts based receptors S1-S3 and the florescence titration plot for S1 with PA. Inset: the solutions of S1 and (S1+PA) in DMSO under UV light. with PA in solution; however, no significant interaction of PA with the anthracene moieties was observed in solution as we well as in the solid state. Also the quenching efficiencies and the Ksv values were correlated with the positive charge(s) present on the receptors with the help of two newly synthesized mono-positive receptors S4 and S5.

Ce travail théorique vise à étudier, via les méthodes Premiers Principes, les propriétés des complexes de métaux de transitions, left[Mleft(dmbpyright)_{3}right]^{n+}nCi^{-} pour un usage en batterie. Pour cette étude ab-initio, les composés mono et bi-nucléaires ont été retenus. La pertinance de notre modélisation a été validée sur les composés mononucléaires. Nous nous sommes interessé au complexes de Fe, Ru et Cu pour lesquels une validation expérimentale était possible. Notre étude a principalement consisté à faire varier les degrés de liberté que nous possédons pour optimiser le voltage et la cinétique de chargement des batteries. Pour cela, nous avons fait varier le TM = Fe, Ru, et Cu, la nature des contre-ions Ci^{-}=PF_{6}^{-}, TFSI^{-} et ClO_{4}^{-} en interaction avec le polymère lors du processus de charge, ainsi que la longeur de la chaîne alkyl qui sépare les deux monomers dans le cas des composés binucléaires. Le composé à base de Fe avec une chaîne -left(CH_{2}right)_{n=6}- a été retenu comme le meilleur candidat pour une application batterie. Le composé à base Ru montre un comportement proche de celui du Fe, quant-au complexe de Cu, il présente des changements de géométrie locale sous chargement trop importants, le rendant peu apte à conduire à une cinétique efficace. Cette étude nous a permis de déterminer que l'approximation PBE était le meilleur choix possible pour modéliser nos complexes dans les conditions de fonctionnement en batterie (dans le champ créé par les contre-ions) et que l'approximation PBE0, généralement utilisée dans la littérature, ne pouvait rendre compte de la physico-chimie de nos composés dans de telles conditions.De surcroît, nous avons dévelopé pour le complexe de Fe, un potentiel atomistique de type “Champ de forces” de manière à pouvoir aborder les aspects dynamiques impliquant de plus grandes tailles de boîte de simulation. Ici, nous modélisons une structure 3D, totalement réticulée à partir de nos monomères à base de Fe. Nous nous sommes servi de la base de donnés DFT que nous avions généré (énergies, géométries, état de spin et fréquences vibrationnelles calculées) pour ajuster les paramètres entrant dans l'écriture du modèle. La construction de la géométrie initiale du polymère 3D a nécessité l'écriture d'un code de calcul visant à produire un arrangement complétement réticulé et à assigner les charges effectives issues des calculs DFT. Ce modèle nous a permis de déterminer les coefficients de diffusion des contre-ions pour les états totalement chargé et non-chargé. Un calcul plus ambitieux vise à déterminer les chemins de diffusion des contre-ions lors d'un processus de chargement en considérant un seul centre de degré d'oxydation 3+ au centre du polymère 3D, pour lequel les centres actifs possèdent un degré d'oxidation 2+. Les contre-ions assurent la neutralité globale.Keyword: Polymer, Electrochemistry, Li-ion Battery, DFT, Force Field development, 3D structure, Atomistic modeling / Abstract Standard redox potentials for mono and bi-nuclear transition metal (TM) complexes left[Mleft(dmbpyright)_{3}right]^{n+}nCi^{-}, have been investigated using First Principles Calculation. Three metal centers are investigated: Fe, Ru, and Cu. Our modeling is validated on mono-nuclear compounds. This approach consists in determining the best small polymer (bi-nuclear) made out of these monomers for a battery application. For that, we varied the three available degrees of freedom i.e., the nature of the central TM atom (Fe, Ru, and Cu), counter-ions Ci=PF_{6}^{-}, TFSI^{-} and ClO_{4}^{-} in interaction with the polymer, and the alkyl chain -left(CH_{2}right)_{n}- of length n that connects both mono-nuclear in the bi-nuclear compound. The Iron compound with -left(CH_{2}right)_{n=6}- is found to be the best candidate. The left[Culeft(dmbpyright)_{2}right]^{n+}nCi^{-} complex shows too much structure deformation upon loading, making it less reliable for cathode material. Moreover, we studied two XC functional, PBE and PBE0 and found, for three complexes PBE approximation retains the ligand field picture whereas PBE0 functional induces an exaggerated and unexpected band dispersion by dissolving the ligand field picture expected for the octahedral environment of the TM in the studied complexes. These findings validate that hybrid functional for which it was designed to localize and cancel self-interaction error does not work for all system. More particularly, the PBE0 approximation fails to model the three complexes (Fe, Ru, and Cu) in functional conditions (in the field made by the counter-ions).Abstract Further, we have developed an atomistic potential relying on the Force Field scheme for the Iron complex in order to study the dynamical properties of this compound at larger simulation scale (3D reticulated polymerization made of our Fe complex monomers). We made an intensive use of our DFT data (energies, geometries, spin-state configurations and calculated vibrational properties) to develop the required parameters entering the model. Moreover, computational techniques (written python language) were developed specifically to create a 3D structure of transition metal complexes satisfying the condition to be fully reticulated. Bounding conditions had to be designed and a procedure aiming at fixing reliable and physical effective charges on each atom of the simulation cell (compatible with DFT results) were developed. Our first simulations have been attached to calculate the diffusion coefficients of the counter-ions in both the fully loaded and unloaded states. A more ambitious and realistic calculation aims at investigating the paths of the counter-ions when one single center starts to be loaded in an unloaded environment.Abstract Keyword: Polymer, Electrochemistry, Li-ion Battery, DFT, Force Field development, 3D structure, Atomistic modeling

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18307号 / 工博第3899号 / 新制||工||1598(附属図書館) / 31165 / 京都大学大学院工学研究科化学工学専攻 / (主査)教授 宮原 稔, 教授 田門 肇, 教授 山本 量一 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Energiförbrukning är ett hett ämne i världen idag, eftersom världens befolkning fortsätter att växa. Som ett resultat ökar också den globala energiförbrukningen snabbt och utsläppen av koldioxid därmed, vilket påverkar global uppvärmning och klimatförändringar. Således kommer utvecklingen av förnybara energikällor att bli en av nödvändighet. Solenergi utgör en förnybar energikälla och uppvisar en enorm potential för att tillgodose det globala energibehovet. En solcell är kan användas för att omvandla solljus till elektricitet. Många typer av solceller har utvecklats under det senaste decenniet, och forskning för att förbättra effektiviteten kommer att fortsätta i framtiden. Material baserade på kopparhalogenidkomplex har uppvisat intressanta optiska och elektrokemiska egenskaper på grund av flera laddningsöverföringsexciterade tillstånd. Genom att kombinera kopparhalogenidsystem med organiska ligander med två bindningsgrupper, kommer komplexet att kunna bilda nätverksstrukturer i flera dimensioner och därmed effektivt kunna leda ström. Eftersom kopparhalogenidkomplex uppvisar unika optiska och elektriska egenskaper, är det värt att undersöka dem för användning i solceller. Syftet med examensarbete har varit att undersöka kopparhalogenidkomplex med optiska och elektrokemiska egenskaper. Kopparhalogenidkomplex med bidentatligander har syntetiserats och applicera som tunna filmer undersöktes. I kapitel 1 och 2 av uppsatsen presenteras bakgrunden och en introduktion av denna studie, samt de experimentella metoderna. I kapitel 3 beskrivs syntesen av kopparjodid-4,4'-bipyridinkomplex och karakteriseringen av detsamma. Applicering av det resulterande materialet på glassubstrat diskuteras också. I kapitel 4 beskrivs syntesen av kopparhalogenid-N-oxid-4,4'-bipyridinkomplex med efterföljande karakterisering. I kapitel 5 undersöks metoder för att applicera kopparjodidpyridin på koppar-folie och FTO-belagda glassubstrat. / Energy consumption is presently a hot topic in the world since the world’s population continues to grow. As a result, global energy consumption is increasing rapidly and the emission of carbon dioxide is also increasing, which causes global warming and climate change. Thus, the development of renewable energy sources will be one of the solutions. Solar energy is one of the renewable energy sources and has a huge potential to satisfy the global energy demand. A solar cell harvests light and converts it to electricity. Many kinds of solar cells have been developed in the past decades, and investigation for the improvement of the efficiency will be continued in the future. Copper halide organic complex materials have some potential for optical and electrochemical properties due to several charge transfer states inside the structure. By combining copper halide with bidentate organic ligands, the complex will form high dimensional network structure and will have electrical property due to the formation of electron conducting paths. Since copper halide complex has potential for unique optical and electrical properties, it is worth investigating for the further photovoltaic application. The aim of the thesis is to investigate copper halide complex material showing optical and electrochemical property. Copper halide complex with bidentate ligands were synthesized and the way to apply copper halide complex to films were also investigated in this thesis. In chapter 1 and 2, the background and the introduction of this study and the experimental methods are presented. In chapter 3, the synthesis of copper iodide 4,4’-bipyridine complex and the characterization of the complex sample are presented. The application of the complex to glass substrate is also discussed. In chapter 4, the synthesis of copper halide N-oxide-4,4’-bipyridine complex and the characterization are discussed. In chapter 5, the way to apply copper iodide pyridine to copper foil and FTO-coated glass substrate is discussed.

No description available.

Two new coordination polymers, DUT-82 and DUT-83 (DUT – Dresden University of Technology), were synthesized by a solvothermal reaction in methanol of rhodium(II) acetate and the tricarboxylic acid H₃btc (btc – benzene-1,3,5-tricarboxylate) or H₃btb (btb – benzene-1,3,5-tribenzoate), respectively. After drying using supercritical carbon dioxide, aerogels with specific surface areas of up to 1150 m² gˉ¹ and pore volumes of up to 2.26 cm³ gˉ¹ were obtained. Although there is no long range order in the materials, the presence of rhodium paddle-wheel units and thus a local order was proven by X-ray absorption spectroscopy measurements. DUT-82 shows good performance in the adsorption of hydrogen and a high affinity for carbon monoxide, which is rarely observed for metal–organic frameworks. Catalytic investigations demonstrate the activity of DUT-82 in the heterogeneous hydrogenation of styrene as a model system. DUT-82 can be recycled for at least ten cycles underlining the stability during the course of reaction.

Die vorliegende Arbeit hat neben der Untersuchung der Synthese über den Controlled SBU-Approach von HKUST-1, ein poröses Kupfertrimesat, die Abscheidung dieses Metal-Organic Frameworks in dünnen Quarzglaskapillaren mit einer Länge von 10 bis 30 m und Innendurchmessern zwischen 0,53 und 0,25 mm zum Thema. Diese Säulen werden zur gaschromatographischen Trennung wie auch zur Bestimmung physikochemischer Kenngrößen, die den Adsorptionsvorgang verschiedener Analyten auf der HKUST-1 Oberfläche beschreiben, verwendet. Zu den untersuchten Stoffen gehören neben unpolaren n-Alkanen, unterschiedlich substituierte Phenylaromaten und starke Lewisbasen, wie Alkoxyalkane. Bei diesen kann der Einfluss der Gestalt und Länge der an den Sauerstoffatomen befindlichen Alkylgruppen auf die Adsorption an HKUST-1 in Form von spezifischen und unspezifischen Wechselwirkungsenthalpien, bestimmt aus gaschromatographischen Messungen, und infrarotspektroskopischen Auswertungen untersucht werden. Abschließend wird eine quantitative Aussage über das Verhältnis von Acidität und Basizität der HKUST-1 Oberfläche getroffen.