The Institute of Resource Ecology (IRE) is one of the eight institutes of the Helmholtz-Zentrum Dresden – Rossendorf (HZDR). The research activities are mainly integrated into the program “Nuclear Waste Management, Safety and Radiation Research (NUSAFE)” of the Helmholtz Association (HGF) and focused on the topics “Safety of Nuclear Waste Disposal” and “Safety Research for Nuclear Reactors”. Additionally, various activities have been started investigating chemical and environmental aspects of processing and recycling of strategic metals, namely rare earth elements. These activities are located in the HGF program “Energy Efficiency, Materials and Resources (EMR)”. Both programs, and therefore all work which is done at IRE, belong to the research sector “Energy” of the HGF. The research objectives are the protection of humans and the environment from hazards caused by pollutants resulting from technical processes that produce energy and raw materials. Treating technology and ecology as a unity is the major scientific challenge in assuring the safety of technical processes and gaining their public acceptance. We investigate the ecological risks exerted by radioactive and nonradioactive metals in the context of nuclear waste disposal, the production of energy in nuclear power plants, and in processes along the value chain of metalliferous raw materials. A common goal is to generate better understanding about the dominating processes essential for metal mobilization and immobilization on the molecular level by using advanced spectroscopic methods. This in turn enables us to assess the macroscopic phenomena, including models, codes, and data for predictive calculations, which determine the transport and distribution of contaminants in the environment.

The framework of this thesis aims to fabricate materials, which change surface characteristics in response to environmental conditions. This response may be employed to improve material characteristics as adhesion, wettability, interaction with cells etc. The mixed brushes introduce adaptive and switching behavior in different surrounding media. Two main approaches were employed to fabricate mixed polymer brushes: "grafting to" and "grafting from". Mixed PS/PVP polymer brushes were synthesized via step-by-step grafting of these two polymers from polyamide (PA) surfaces. NH3 plasma was used for the introduction of amino and OH functionalities on PA surfaces with following attachment of azo initiator of radical polymerizaton. The mixed brushes prepared on the surface of PA textiles combine both the switching effect and effect of composite surface (i.e. micrometer scale roughness) which substantially amplifies the switching range. Mixed polymer brushes prepared from P(S-b-2VP-b-EO) and P(S-b-4VP) block copolymers were grafted to both the flat surface of Si wafers and to the surface of silica nanoparticles via quaternization reaction of the pyridine nitrogen. This one step grafting technique has a substantial advantage over the multistep grafting of mixed polymer brushes. We have demonstrated that combination of the two level hierarchical organization of polymer films at macroscopic and nanoscopic levels resulted in the formation of self adaptive surfaces switchable in controlled environment from ultra-hydrophobic to hydrophilic energetic states. The PFS/PVP mixed brush was grafted onto the pre-treated PTFE surface (plasma etching) with the needle like topography. The size of vertical needles was at micron scale. If the brush is switched to the hydrophobic state the layer has shown a unique ultra-hydrophobic behavior (complete non-wetting) with the contact angle approaching value of 160o. If the mixed brush was switched into the hydrophilic state the surface became completely wetted due to the capillary forces in the pores formed by the needle like structure. Thus, the surface can be either highly wettable or completely non-wettable with the self cleaning properties.

Die ITRS (International Technology Roadmap for Semiconductors) sagt voraus, dass die fortlaufende Miniaturisierung der Transistoren und Verdrahtungen auch neue Isolationsmaterialien mit äußerst niedrigen (ultralow) Dielektrizitätskonstanten k erfordern wird. Die Miniaturisierung der Bauteile der ULSI (Ultra Large Scale Integration) führt zu starken Anforderungen an die Fertigung der kritischen Bereiche (backend-of-line, BEoL). Die ITRS deutet darauf hin, dass die k-Werte bis zu 2.0 für die 45 nm Technologie reduziert werden müssen, und zu noch niedrigeren k-Werten (k  1.5) für die nachfolgenden Jahre. Ergänzend zur äußerst niedrigen dielektrischen Konstante müssen die Isolatoren auch über entsprechende mechanische Eigenschaften verfügen. Die vorliegende Arbeit stellt Forschungen vor, die das Ziel haben, mittels modernen ab-initio und halbempirischen theoretischen Methoden neuartige Isolationsmaterialien für zukünftige mikroelektronische Anwendungen zu entwerfen. Die umfangreichen eingesetzten Rechenmethoden wurden verwendet, um strukturelle und physikalische (mechanische, dielektrische und elektronische) Eigenschaften von entworfenen Zwischenschichtsdielektrika zu bestimmen. Eine neue Art von Materialien wird vorgestellt, die als ein möglicher Kandidat für isolierende ultralow-k dünne Schichte zwischen Metallleiterbahnen in zukünftigen CMOS (Complementary Metal-Oxide-Semiconductor) Technologien fungieren sollen. Die Struktur der neuartigen Materialien wird durch ein Modell beschrieben, das ein geordnetes dreidimensionales Netzwerk (Mosaikstruktur) darstellt. Dies besteht aus drei Hauptkomponenten: Knoten, Kanten und Topologie der Anordnung. Fullerenmoleküle (C60) werden als Knoten des Netzwerkes verwendet. Die Knoten werden durch Verknüpfermoleküle entlang der Kanten der Mosaikzelle angekoppelt. Dies wird durch kovalente Bindungen realisiert. Als Verknüpfermoleküle werden Kohlenwasserstoff- Kettenmoleküle verwendet. Einfache kubische, flächenzentrierte kubische und diamantähnliche Topologien werden für Anordnungen des Netzwerkes betrachtet. Das Innere einer Netzwerkzelle repräsentiert eine Nanopore der Größe in Bereich von 1 nm. Zunächst werden am Beispiel fluorierter Fullerene Probleme der molekularen Polarisierbarkeit untersucht. In Molekülen mit ionischem Beitrag zur Bindung kann der Beitrag der Kernverschiebungen (wegen des äußeren Feldes) zur statischen Polarisierbarkeit entscheidend sein. Mittels der Finite Field Methode wird die Struktur mit und ohne ein endliches äußeres elektrisches Feld optimiert. Dabei wird die Optimierung durch Minimierung der Gesamtenergie durchgeführt und die molekulare Polarisierbarkeit aus dem induzierten Dipolmoment bestimmt. In C60Fn erhöht meistens das Fluorieren die Polarisierbarkeit. Nur für n = 2 und 18, wobei das Molekül ohne ein äußeres Feld ein sehr großes Dipolmoment hat, wird die Polarisierbarkeit verringert. Für große Werte n (n = 20, 36 und 48) wird die Polarisierbarkeit pro zusätzliches Fluoratom wegen Kernverschiebungen deutlich erhöht. Die Modifizierung der Knoten des Netzwerkes wird betrachtet und die Anwendbarkeit des Additivitätsmodells diskutiert. Die Dielektrizitätskonstante des reinen flächenzentrierten kubischen Fullerengitters beträgt etwa 4.4. Die Einführung der Verknüpfermoleküle zwischen benachbarten Fullerenmolekülen und die gleichzeitige Verwendung von auf Kohlenstoffatomen basierten käfigförmigen Molekülen reduziert die Dichte des Materials. Dies ergibt eine beträchtliche Verringerung der makroskopischen Polarisierbarkeit des Materials. Die Struktureinheit, die aus zwei Fullerenmolekülen und einem Kohlenwasserstoff-Verknüpfermolekül besteht, wird mittels quantenchemischer Methoden (DFTB Molekulardynamik) optimiert. Es werden die Dichte der lokalen Dipole und elektronische Effekte betrachtet, um die effektive Dielektrizitätskonstante des Modells abzuschätzen. Die Berechnungen zeigen, dass k-Werte von etwa 1.4 erreicht werden können, wenn C6H12 Kettenmoleküle verwendet werden, um die C60-Moleküle im Netzwerk mit diamantähnlicher Symmetrie zu verknüpfen. Weiterhin werden molekulare Cluster mit angelegten periodischen Randbedingungen für einfache kubische und diamantähnliche Topologien konstruiert. Kombinationen der klassischen und quantentheoretischen Methoden werden eingesetzt, um die Struktur zu optimieren, Kompressionsmodule zu berechnen und die dielektrischen Eigenschaften der fullerenbasierten Materialien zu berechnen. Dies hat das Ziel, ultralow-k Isolatoren mit entsprechenden mechanischen Eigenschaften zu finden. Es wird die kovalente Verknüpfung der C60 Moleküle untersucht und sowohl die Länge und chemische Zusammensetzung des Verknüpfermoleküles als auch die Verknüpfungsgeometrie variiert. Gemäß dem entworfenen Modell werden Strukturen mit einfacher kubischer und diamantähnlicher Topologie des Netzwerkes als vielversprechende Kandidaten betrachtet. Die (statische) Dielektrizitätskonstanten k und Kompressionsmodule B sind für einige vorgeschlagene Materialien im Bereich von k = 1.7 bis 2.2 und beziehungsweise von B = 5 bis 23 GPa. Das Clausius-Mossotti Modell wird zur Bestimmung der Dielektrizitätskonstante der entworfenen Strukturen verwendet. In den nächsten Schritten der Arbeit werden die Wege der Verbesserungen für das vorgeschlagene Modell betrachtet. Es wird analysiert, auf welche Art Verknüpfermoleküle an die Knoten gebunden werden können, um die mechanischen und dielektrischen Eigenschaften der generierten ultralow-k Strukturen zu verbessern. Es gibt zwei mögliche verschiede Arten, die Verknüpfermoleküle > C = C < und > C – CH2 – CH2 – C < an das Käfigmolekül C60 anzukoppeln. Die Berechnungen zeigen, dass es im gegenwärtigen Verbesserungsschritt möglich ist, für die einfache kubische Topologie Eigenschaftskombinationen mit k = 2.2 und B = 33 GPa zu bekommen. In der vorliegenden Arbeit wurde eine theoretische Methode ¬¬– sogenannter molekularer Entwurf – entwickelt und erfolgreich angewandt. Die theoretische Behandlung ist kompliziert, weil Wechselwirkungen im atomaren Skalabereich und auf einem strukturellen Niveau von 1 nm zusammen betrachtet werden müssen. Dies Verfahren erfordert die Anwendung komplementärer theoretischen Methoden, um das gesamte Problem beschreiben zu können. Die Methoden schließen klassische, kontinuierliche theoretische und quantenchemische Näherungen ein. Der Vorteil dieser Methode ist, dass verschiedene mögliche Kandidaten für ultralow-k Dielektrika theoretisch getestet werden können, ohne teure und zeitaufwendige Experimente durchzuführen. / The International Technology Roadmap for Semiconductors (ITRS) predicts that continued scaling of devices will require insulating materials with ultralow dielectric constant k. The shrinking of device dimensions of ultra-large-scale integrated (ULSI) chips imposes strong demands on the backend of the line (BEoL) interconnect structures. The ITRS indicates that the k values need to be reduced to 2.0 for the 45 nm technology node or below (k  1.5) in the next few years. Additionally to extremely low dielectric constants, the insulating materials must have also suitable mechanical properties. The work represents research, which is aimed to support molecular design and investigations of modelled novel insulating materials for future application in microelectronics by means of theoretical ab-initio and semiempirical methods. A wide range of computational methods were used to estimate structural and physical (mechanical, dielectrical and electronic) properties of the designed interlayer dielectrics (ILDs). A new class of materials is presented that is supposed to be a potential candidate for isolating ultralow-k thin films between metal on-chip interconnects in future CMOS technology nodes. The structure of the novel materials is described by a model that assumes an ordered three-dimensional network (mosaic structure) consisting of three main components: nodes, edges and topology of arrangement. Fullerene (C60) molecules are used as the nodes of the network. The nodes are connected by linker molecules along the edges of the mosaic cells through a covalent bonding. Hydrocarbon chain molecules are used as the linkers. Simple cubic, face-centred cubic and diamond-like topologies of the network are considered. The interior of a network cell represents a nanopore of a 1-nm scale. At first problems of molecular polarizability are investigated considering the case of fluorinated fullerenes. In molecules with ionic contribution to the binding, the contribution of nuclear displacements (due to the external field) to the static polarizability can be decisive. Using the finite field method, the structure is optimized with and without a finite external electric field by a total energy minimization and the polarizability is calculated from the induced dipole moment. In C60Fn, fluorination mostly increases the molecular polarizability. Only for n = 2 and 18, where the molecule without an external field has a very large dipole moment, fluorination does decrease it. For large n (n = 20, 36, and 48), the polarizability per added F atom due to nuclear displacements is increased by a factor of about 2. The modification of the nodes of the network is considered and the validity of the additivity model is discussed. The dielectric constant of the pure fullerene face-centred cubic lattice is about 4.4. The introduction of bridge molecules between neighbouring fullerene molecules and the simultaneous usage of cage-like molecules based on carbon atoms reduces the density of the material. This results in a considerable decrease of the macroscopic polarizability of the material. The structural units of the models consisting of two fullerenes and a hydrocarbon bridge molecule are optimized by means of quantum chemical methods (DFTB molecular dynamics). The density of local dipoles and electronic effects are considered to estimate the effective dielectric constant of the models. It is shown that k values of about 1.4 can be obtained if C6H12 chain molecules are used to connect C60 molecules on a network with diamond-like symmetry. Further, molecular clusters with applied periodic boundary conditions are constructed for simple cubic and diamond-like topologies. Combinations of classical and quantum-theoretical approaches are used to optimize the structure, to calculate bulk moduli, and for the assessment of the dielectric properties of fullerene-based materials with the goal to find ultralow-k insulators with suitable mechanical properties. The covalent linking of C60 molecules is studied and the length and chemical composition of the linker molecule as well as the linkage geometry is varied. According to the molecular design-based model, structures with simple cubic and diamond-like topology of the network are proposed as promising candidates. The (static) dielectric constants k and elastic bulk moduli B of the proposed materials are in the range of k = 1.7 to 2.2 and B = 5 to 23 GPa, respectively. The Clausius-Mossotti-Model is used to estimate dielectric constants of the designed structures. In the next steps of the work the ways of improvements for the proposed model are considered. The way to connect linker molecules to the node molecules is analyzed, in order to improve the mechanical and dielectric properties of the generated ultralow-k structures. Two different types of bonding linker molecules to the cage C60 molecule with the > C = C < and > C – CH2 – CH2 – C < linker molecules are possible. It is shown that at the present improvement step it is possible to get property combinations with dielectric constant of k = 2.2 and bulk modulus of B = 33 GPa for the simple cubic topology. In this work a theoretical method called molecular design is developed and successfully applied. The theoretical treatment is difficult since interactions both on the atomic scale and on the structural level of 1 nm must be considered. This approach requires the application of complementary theoretical methods to describe the complex problems. The methods include classical, continuum theoretical and quantum-chemical approximations. The advantage of the present approach is that various possible candidates for ultralow-k dielectrics can be tested theoretically without performing expensive and time-consuming experiments.

In this study a series of novel Fe-based materials derived from a bulk metallic glass-forming composition was investigated to improve the ductility of this high-strength glassy alloy. The interplay between the factors chemistry, structure and resulting mechanical properties was analyzed in detail. It has been recognized that subtle modifications of the chemical composition (carbon addition) lead to appreciable changes in the phase formation, which occurs upon solidification (from a single-phase structure to composite materials). As a consequence, significant differences in the mechanical response of the particular samples have been observed. The materials developed here were fabricated by centrifugal casting. To explore the structure features of the as-cast cylinders, manifold experimental techniques (X-ray diffraction, optical, as well as electron microscopy) were employed. The occurrence of the numerous reflections on the X-ray diffraction patterns has confirmed the crystalline nature of the studied Fe-based alloy systems. The subsequent extensive research on their deformation behavior (Vickers hardness and room temperature compression tests) has revealed that, although the glass-forming ability of the investigated compositions is not high enough to obtain a glassy phase as a product of casting, excellent mechanical characteristics (high strength - comparable to that of the reference bulk metallic glass (BMG) - associated with good ductility) were achieved for the “composite-like” alloys. In contrast, the single phase cylinders, subjected to compressive loading, manifested an amazing capacity for plastic deformation – no failure occurred. The fracture motives developed during deformation of the “composite-structured” samples were studied by scanning electron microscopy. The main emphasis has been put on understanding the mechanisms of crack propagation. Owing to the structural complexity of the deformed samples, it was crucial to elucidate the properties of the individual compounds. Based on the obtained results it was concluded that the coexistence of a soft f.c.c. γ-Fe phase in combination with a hard complex matrix is responsible for the outstanding mechanical response of the tested composites. While the soft particles of an austenite contribute to the ductility (they hinder the crack propagation and hence, cause unequivocal strain-hardening), the hard constituents of the matrix phase yield the strength.

Wasserstoff ist der ideale Energieträger, da er völlig schadstofffrei verbrennt und einen potentiell hohen Energiegehalt pro Masse besitzt. Die größte Herausforderung für den Gebrauch von Wasserstoff als Kraftstoff ist die Wasserstoffspeicherung in sicheren und kostengünstigen Systemen. Die Ziele und Aufgaben der vorliegenden Doktorarbeit sind, poröse Materialien, die unterschiedliche Struktur und Zusammensetzung besitzen, für die Physisorption von Wasserstoff mittels einer neuartigen volumetrischen Apparatur zu untersuchen. Das Erreichen maximaler Speicherdaten stand nicht im Vordergrund dieser Arbeit. Viel wichtiger war es, einen Struktur – Eigenschafts – (Sorptions) – Zusammenhang zu verstehen, auf deren Basis eine systematische Entwicklung von Wasserstoffspeichermaterialien erfolgen könnte. Zwei Klassen von potentiellen Wasserstoffspeichern wurden erforscht: expandierte Graphitmaterialien und Metallorganische Netzwerke. Neue experimentelle Methoden zur Untersuchung der Wasserstoffspeicherkapazität an modifizierter volumetrischer Apparatur wurden erfolgreich entwickelt und geprüft. Das Verwenden einer der Kammern als Referenzkammer ermöglicht das Ausschließen der experimentellen Artefakte aus der Auswertung der gespeicherten Wasserstoffmenge. Es wurde keine Gaszustandgleichung bei tiefen Temperaturen verwendet, was sehr wichtig bei den Experimenten mit Wasserstoff ist.

Ferroelectric HfO₂ attracts a huge amount of attention not only for memory and negative capacitance, but also for programmable logic including memory-in-logic and neuromorphic applications. However, the understanding of material fundamentals still needs to be improved. This paper gives material fundamentals and new insights to this ferroelectric material for future device applications. In particular, the key role of dopants, effects of the interface on the ferroelectric phase, and a detailed discussion of the switching kinetics are of central focus. Based on material properties newly obtained, we discuss opportunities of ferroelectric HfO₂ for device applications.

Beschäftigte im öffentlichen Dienst sind einer steigenden Zahl von Übergriffen und Bedrohungen ausgesetzt. Auch in den Statistiken der Unfallversicherungsträger und der Polizei findet sich das Phänomen Gewalt verstärkt wieder. Die Wahrscheinlichkeit einer Verletzung durch eine Stichwaffe ist in Deutschland deutlich höher einzustufen als die mittels einer Schusswaffe bzw. einem Projektil. Zudem werden stichhemmende und Stichschutzwesten nicht nur für den Einsatz im behördlichen, militärischen und Sicherheitsbereich angeboten, sondern auch für Privat- und Geschäftsleute. Die Westen sollen die Träger vor Angriffen mit Messern, Nadeln und spitzen Gegenständen schützen, sind jedoch in ihrem Tragekomfort verbesserungswürdig. Derzeit erfolgt die Abschwächung von Angriffen mit Stichwaffen durch integrierte Schutzplatten aus Aluminium, Edelstahl, Kunststoff, Keramik und/oder Metall-Ringgeweben. Die Stichschutzwesten besitzen zum einen ein beträchtliches Gewicht (je nach Modell und Größe 1,5 bis 5 kg). Zum anderen weisen sie bei langer Tragedauer und hohen Außentemperaturen (z. B. während der Sommermonate) ein schlechtes thermophysiologisches Verhalten auf. Üblicherweise nimmt die Schutzwirkung mit steigendem Gewicht zu. Eine Gewichtserhöhung vermindert jedoch den Tragekomfort, wodurch auch die Trageakzeptanz, d. h. die Bereitschaft einer Person zum Tragen der Schutzkleidung, verringert wird. Diese Trageakzeptanz stellt ein entscheidendes Kriterium für den erfolgreichen Personenschutz dar. Einen möglichen Lösungsansatz bietet die Realisierung von Leichtbaupotenzialen mittels neuer Technologien und hybriden Materialien. Durch eine Überarbeitung des bisherigen Designs der Schutzkleidung soll der Tragekomfort unter Beibehaltung der Funktionalität deutlich verbessert werden. Statt der bisher angewandten Schutzplatten wird eine körperformabhängige Segmentierung von bioinspirierten Interlocking-Strukturen aus Hochleistungsfaserstoffen entwickelt. Die Verstärkungskomponente mit hoher Schlagzähigkeit, Bruchdehnung und Zugfestigkeit besteht aus Aramidfasern. Zudem werden die Stichschutzelemente mittels additiver Fertigung auf biegeweiche Maschenwaren appliziert. Die Schutzkleidung lässt sich an die jeweilige Körperform anpassen und bietet neben dem Stichschutz einen verbesserten ergonomischen, thermophysiologischen sowie hautsensorischen Komfort. [... aus der Einleitung]

Electrocatalysis plays a prominent role in renewable energy conversion and storage, enabling a number of sustainable processes for future technologies. There are generally three strategies to improve the efficiency (or activity) of the electrocatalysts: (i) increasing the intrinsic activity of the catalyst itself; (ii) improving the exposure of active sites; and (iii) acceleratingmass transfer during catalysis (both reactants and products). These strategies are not mutually exclusive and can ideally be addressed simultaneously, leading to the largest improvements in activity. Aerogels, as featured by large surface area, high porosity, and self-supportability provide a platform that matches all the aforementioned criteria for the design of efficient electrocatalysts. The field of aerogel synthesis has seen much progress in recent years, mainly thanks to the rapid development of nanotechnology. Employing precursors with different properties enables the resulting aerogel with targeted catalytic properties and improved performances. This report demonstrates the design strategies of aerogel catalysts and reviews their performances for several electrochemical reactions. The common principles that govern electrocatalysis are further discussed for each category of reactions, thus serving as a guide to the development of future aerogel electrocatalysts.

An environment is defined by a set of field values, such as temperature, electro-magnetic field, light intensity, air humidity and air composition. Smart materials, such as hydrogels, are able to react to these kinds of stimuli. The spatial and time development of environmental values is governed by transport equations. Hence the reaction, i.e. actuation or sensing, of the smart material can be described based on the same assumptions. The displacement, here swelling and deswelling, of the material depends on the combination of the environmental parameters. Smart materials are called multi-sensitive, when more than one parameter is purposely used (i) to manipulate the material, i.e. as an actuator or (ii) to measure the quantities, i.e. as a (multi-)sensor. However, the material can also perform (iii) the objective of a logic processing unit in addition to (i) and (ii). In the current work, we present a device that realizes this concept: An automatic window opener that senses environmental parameters (light-level and air temperature) and reacts accordingly. The hydrogel material that is included in the simplistic device simultaneously acts as sensor, logic processing unit and actuator.

Metal-organic framework (MOF) compounds as a new class of porous coordination polymers consists of metal ions or clusters linked by organic molecules. They have gained recent interest because of their large surface areas and huge variety of the porous network structures. They exhibit interesting adsorption properties and therefore are potential candidates for various technical applications. In this work, continuous wave (cw) and pulsed electron paramagnetic resonance (EPR) methods such as pulsed electron-nuclear double resonance (ENDOR) and hyperfine sublevel correlation (HYSCORE) spectroscopy are applied to study metal-organic frameworks with respect to different aspects of their properties: The host-guest interactions between Cu2+ ions in [Cu3(btc)2]n (HKUST-1; btc: 1,3,5-benzenetricaboxylate) with adsorbed methanol (CH3OH), 13C enriched carbon monoxide and dioxide (13CO, 13CO2), hydrogen (H2), deuterium (D2) and mixed isotopic HD. In [Cu3(btc)2]n, the Cu2+ ions are connected to binuclear Cu/Cu paddle wheel units. Since the Cu2+ ions in the [Cu3(btc)2]n are antiferromagnetically coupled, the new compound [Cu2.97Zn0.03(btc)2]n is synthesized by isomorphous substitution containing about 1 % paramagnetic Cu/Zn paddle wheel units. The modified Cu/Zn paddle wheel units prove to be a very sensitive probe for the interactions with the adsorbed molecules. Secondly, the exchange interactions of antiferromagnetically coupled Cu/Cu paddle wheel units as well as additional inter-paddle wheel exchange interactions between the Cu/Cu pairs are studied in [Cu2(bdc)2(dabco)]n, a layered MOF with 1,4-benzenedicaboxylate (bdc) as linker and 1,4-diazabicyclo[2.2.2]octane (dabco) acting as pillars between the layers. In comparison to [Cu3(btc)2]n, the additional inter-paddle wheel exchange interactions are much easier disturbed by incorporation of Zn2+ ions into the framework structure. Third, the structural dynamics of the framework is investigated in the compound [Al(OH)(bdc)]n (MIL-53) which was isomorphously substituted by V(III)/V(IV) species. The 51V hyperfine structure revealed to be sensitive to the so-called breathing effect, a flexible structural behaviour upon guest adsorption/desorption or upon thermal treatment. It is shown that the aluminum ions can be substituted by vanadium but the octahedral coordination environment changes slightly to a pseudo-octahedral or a square-pyramidal coordination. Based on the hyperfine interactions between the electron spin and the nuclear spins of the surrounding atoms, structural models can be derived from orientation-selective measurements. In such a way, structural information of materials like powder samples and adsorbate complexes can be obtained which are hardly or even not accessible by other methods.:1 Introduction 1.1 Electron paramagnetic resonance spectroscopy for investigation of porous materials 1.2 Metal-organic frameworks 1.3 Implementation of paramagnetism by isomorphous substitution 1.4 EPR spectroscopic methods 1.4.1 Spin Hamiltonian 1.4.2 cw EPR spectroscopy 1.4.3 Pulsed EPR spectroscopy 1.5 Description of the project 2 [Cu2.97Zn0.03(btc)2]n 2.1 Introduction: Monometallic [Cu3(btc)2]n (1) 2.1.1 Spin coupling 2.1.2 Adsorption of H2O 2.1.3 Adsorption of DTBN 2.2 Isomorphous substitution of Cu2+ by Zn2+ in [Cu3(btc)2]n 2.2.1 Synthesis and characterisation of [Cu2.97Zn0.03(btc)2]n (2) 2.2.2 cw EPR spectroscopy of 2 2.2.3 Pulsed EPR spectroscopy of 2 2.2.4 Summary: Zn2+ substitution 2.3 Adsorption of methanol (MeOH) on [Cu2.97Zn0.03(btc)2]n (2_MeOH) 2.3.1 cw EPR spectroscopy of 2_MeOH 2.3.2 Pulsed EPR spectroscopy of 2_MeOH 2.3.3 Discussion 2.3.4 Summary: adsorption of MeOH 2.4 Adsorption of 13CO2 and 13CO on [Cu2.97Zn0.03(btc)2]n (2_CO2, 2_CO) 2.4.1 cw EPR spectroscopy of 2_CO2 and 2_CO 2.4.2 Pulsed EPR spectroscopy of 2_CO2 and 2_CO 2.4.3 Discussion 2.4.4 Summary: adsorption of 13CO2 and 13CO 2.5 Adsorption of H2, D2 and HD on [Cu2.97Zn0.03(btc)2]n (2_HH, 2_DD and 2_HD) 2.5.1 cw EPR spectroscopy of 2_HH, 2_DD and 2_HD 2.5.2 Pulsed EPR spectroscopy of 2_HH, 2_DD and 2_HD 2.5.2.1 3p ESEEM spectroscopy of 2_HH, 2_DD and 2_HD 2.5.2.2 Davies-ENDOR spectroscopy of 2_HH 2.5.2.3 Davies-ENDOR spectroscopy of 2_HD 2.5.2.4 Davies-ENDOR spectroscopy of 2_DD 2.5.3 Discussion 2.5.4 Summary: adsorption of H2, D2 and HD 2.6 Conclusion: [Cu2.97Zn0.03(btc)2]n 3 [Cu2(bdc)2(dabco)]n (3) and [Cu(2-x)Zn(x)(bdc)2(dabco)]n (3_x) 3.1 [Cu2(bdc)2(dabco)]n (3) 3.2 [Cu1.9Zn0.1(bdc)2(dabco)]n (3_0.1) 3.3 [Cu(2-x)Zn(x)(bdc)2(dabco)]n (3_0.5, 3_1.0, 3_1.5 and 3_1.9) 3.4 Determination of the exchange coupling constant J 3.5 Discussion 3.6 Conclusions: [Cu(2-x)Zn(x)(bdc)2(dabco)]n (3_x) 4 [(AlOH)1-x(VO)x(bdc)]n (4) and [(AlOH)1-x(VO)x(ndc)]n (5) 4.1 Introduction 4.2 EPR spectroscopic investigations of mixed-metal bdc compounds 4.3 EPR spectroscopic investigations of mixed-metal ndc compounds 4.4: Conclucions: V(III)/V(IV) substitution in [Al(OH)(bdc)]n and [Al(OH)(ndc)]n 5 Summary and Conclusion 5.1 Host-guest interactions 5.2 Exchange couplings of Cu/Cu pairs 5.3 Structural dynamics of the bdc and the ndc framework 5.4 Conclusion 6 Appendix 6.1 Experimental details and additional spectra 6.2 Instrumental details 6.3 Curriculum vitae and publications