This Thesis presents studies of molecular association in aqueous solution and at the liquid/solid interface. The investigated molecular systems range from self-aggregating surfactants to hydration water in contact with micelles or individual molecules. In most studies, combinations of various NMR methods were applied. These vary from simple chemical shift and intensity measurements to more elaborate self-diffusion and intermolecular cross-relaxation experiments. Non-ideal mixed micelles of fluorinated and hydrogenated surfactants were studied by an experimental procedure that allows an analysis in terms of micellar structure, using a minimal number of initial assumptions. Quantitative conclusions about micro-phase separation within mixed micelles were obtained within the framework of the regular solution theory. Additionally, NMR was introduced and developed as a powerful method for studying adsorption of surfactants at solid interfaces. Adsorption isotherms for pure and mixed surfactant systems and non-ideal mixing behavior of fluorinated and hydrogenated surfactants at solid surfaces were quantified. Fluorosurfactant-protein association was investigated using the methods described. Intermolecular cross-relaxation rates between solute and solvent molecules were recorded at several different magnetic fields. The results reveal strong frequency dependence for both small molecules and micelles. This finding demonstrates that intermolecular cross-relaxation is not solely controlled by fast local motions, but also by long-range translational dynamics. Data analysis in terms of recently developed relaxation models provides information about the hydrophobic hydration and micellar structure. / QC 20100914

This thesis is about using nuclear magnetic resonance (NMR) spectroscopy for studying soft materials. Soft materials may be encountered everyday by most readers of this thesis, for example when taking a shower or watching TV. The usefulness of these materials originates from them being soft yet, at the same time, having some kind of a structure. The characteristic length scale of those structures is often on the order of nanometers (10-9 m) and the structure can respond to various external stimuli such as temperature, electric and magnetic fields, or the presence of interfaces. NMR spectroscopy excels when studying soft materials because it is a non-invasive technique with a large spectral resolution. Moreover, different NMR methods allow us to study local molecular dynamics or longer-range translational diffusion. Understanding those latter aspects is very important for the development of dynamic and responsive materials. Papers I-III present our work on assessing molecular adsorption on interfaces in colloidal dispersions. Here, carbon nanotubes (CNTs) or silica particles were the colloidal substrates to which proteins, polymers or surfactants adsorbed. Papers IV-VI concern ionic mobility in liquid crystals (LCs). The influence of material structure on, for example, the anisotropy of diffusion or on the association/dissociation of ions was studied in several LC phases. / QC 20110225

To enable future environmentally friendly access to space by means of solid rocket propulsion a viable replacement to the hazardous ammonium perchlorate oxidizer is needed. Ammonium dinitramide (ADN) is one of few such compounds currently known. Unfortunately compatibility issues with many polymer binder systems and unexplained solid-state behavior have thus far hampered the development of ADN-based propellants. Chapters one, two and three offer a general introduction to the thesis, and into relevant aspects of quantum chemistry and polymer chemistry. Chapter four of this thesis presents extensive quantum chemical and spectroscopic studies that explain much of ADN’s anomalous reactivity, solid-state behavior and thermal stability. Polarization of surface dinitramide anions has been identified as the main reason for the decreased stability of solid ADN, and theoretical models have been developed to explain and predict the solid-state stability of general dinitramide salts. Experimental decomposition characteristics for ADN, such as activation energy and decomposition products, have been explained for different physical conditions. The reactivity of ADN towards many chemical groups is explained by ammonium-mediated conjugate addition reactions. It is predicted that ADN can be stabilized by changing the surface chemistry with additives, for example by using hydrogen bond donors, and by trapping radical intermediates using suitable amine-functionalities. Chapter five presents several conceptual green energetic materials (GEMs), including different pentazolate derivatives, which have been subjected to thorough theoretical studies. One of these, trinitramide (TNA), has been synthesized and characterized by vibrational and nuclear magnetic resonance spectroscopy. Finally, chapter six covers the synthesis of several polymeric materials based on polyoxetanes, which have been tested for compatibility with ADN. Successful formation of polymer matrices based on the ADN-compatible polyglycidyl azide polymer (GAP) has been demonstrated using a novel type of macromolecular curing agent. In light of these results further work towards ADN-propellants is strongly encouraged. / QC 20101103

Energy from the sun can be converted to low cost electricity using dye-sensitized solar cells (DSCs). Dye molecules adsorbed to the surface of mesoporous TiO2 absorb light and inject electrons into the semiconductor. They are then regenerated by the reduced redox species from an electrolyte, typically consisting of the iodide/tri-iodide redox couple in an organic solvent. In a solid state version of the DSC, the liquid electrolyte is replaced by an organic hole conductor. Solid state DSCs using 2,2'7,7'-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9'-spirobifluorene (spiro-MeOTAD) have reached conversion efficiencies of up to 6 %, which is about half of the efficiency of the best iodide/tri-iodide cells.   Measurement techniques, such as spectroelectrochemistry and photo-induced absorption spectroscopy (PIA), were developed and applied to study the working mechanism of organic dyes in solid state DSCs under solar cell operating conditions. The energy alignment of the different solar cell components was studied by spectroelectrochemistry and the results were compared to photoelectron spectroscopy. PIA was used to study the injection and regeneration processes. For the first time, it was shown here that the results of PIA are influenced by an electric field due to the electrons injected into the TiO2. This electric field causes a shift in the absorption spectrum of dye molecules adsorbed to the TiO2 surface due to the Stark effect.   Taking the Stark effect into consideration during the data analysis, mechanistic differences between solid state and conventional DSCs were found. A perylene dye, ID176, was only able to efficiently inject electrons into the TiO2 in presence of lithium ions and in absence of a solvent. As a result, the sensitiser worked surprisingly well in solid state DSCs but not in liquid electrolyte ones. Regeneration of oxidised dye molecules by spiro-MeOTAD was found to be fast and efficient and spiro-MeOTAD could even reduce excited dye molecules.

Processes where a molecule absorbs visible light and then converts the solar energy into chemical energy are important in many biological systems, such as photosynthesis and also in many technical applications e.g. photovoltaics. This thesis describes a part of a multidisciplinary project, aiming at a functional mimic of the natural photosynthesis, with the overall goal of production of a renewable fuel from sun and water. More specific, the thesis is focused on design and photophysical characterization of new photosensitizers, i.e. light absorbers that should be capable of transferring electrons to an acceptor and be suitable building blocks for supramolecular rod-like donor-photosensitizer-acceptor arrays. The excited state lifetime, the excited state energy and the geometry are important properties for a photosensitizer. The work presented here describes a new strategy to obtain longer excited state lifetimes of the geometrically favorable Ru(II)-bistridentate type complexes, without a concomitant substantial decrease in excited state energy. The basic idea is that a more octahedral coordination around the Ru will lead to longer excited state lifetimes. In the first generation of new photosensitizers a 50-fold increase of the excited state lifetime was observed, going from 0.25 ns for the model complex to 15 ns for the best photosensitizer. The second generation goes another step forward, to an excited state lifetime of 810 ns. Furthermore, the third generation of new photosensitizers show excited state lifetimes in the 0.45 - 5.5 microsecond region at room temperature, a significant improvement. In addition, the third generation of photosensitizers are suitable for further symmetric attachment of electron donor and acceptor motifs, and it is shown that the favorable properties are maintained upon the attachment of anchoring groups. The reactivity of the excited state towards light-induced reactions is proved and the photostability is sufficient so the new design strategy has proven successful.

Iron oxyhydroxide (FeOOH) mineral plays an important role in a variety of atmospheric, terrestrial and technological settings. Molecular resolution of reactions involving these minerals is thereby required to develop a fundamental understanding of their contributions in processes taking place in the atmosphere, Earth’s upper crust as well as the hydrosphere. This study resolves interactions involving four different types of synthetic FeOOH particles with distinct and well-defined surfaces, namely lath- and rod-shaped lepidocrocite (γ), goethite (α) and akaganéite (β). The surface and bulk reactivities of these particles are controlled by their distinct structures. When exposed to ambient atmospheric or aqueous conditions their surfaces are populated with different types of (hydr)oxo functional groups acting as reaction centers. These sites consist of hydroxyl groups that can be singly- (≡FeOH, -OH), doubly- (≡Fe2OH, μ-OH), or triply-coordinated (≡Fe3OH, μ3-OH) with underlying Fe atoms. Moreover, these sites exhibit different types, densities, distributions, as well as hydrogen bonding patterns on different crystal planes for each mineral. Knowledge of the types and distributions of hydroxyl groups on minerals with different surface structures is fundamental for building a molecular-scale understanding of processes taking place at FeOOH particle surfaces. In this thesis, Fourier transform infrared (FTIR) spectroscopy was used to resolve the interactions between (hydr)oxo groups of FeOOH particles with (in)organic acids, salts, water vapor as well as carbon dioxide. The focus on such compounds was justified by their importance in natural environments. This thesis is based on 9 articles and manuscripts that can be found in the appendices. FTIR spectroscopic signatures of hydroxyl groups in the bulk of well crystallized FeOOH minerals were characterized for structural differences and thermal stabilities. Those of akaganéite were particularly resolved for the variable bond strength of bulk hydroxyls induced by the incorporation of HCl through nanostructured channels at the terminations of the particles. FTIR bands of hydroxyl groups at all particle surfaces were monitored for responses to thermal gradients and proton loadings, providing experimental validation to previous theoretical accounts on surface site reactivity. This site reactivity was resolved further in the fluoride (F-) and phosphate (PO43-) ions adsorption study to follow the site selectivity for ligand-exchange reactions. These efforts showed that singly-coordinated groups are the primary adsorption centers for ligands, doubly-coordinated groups can only be exchanged at substantially higher ligand loadings, while triply coordinated groups are largely resilient to any ligand-exchange reaction. These findings helped consolidate fundamental knowledge that can be used in investigating sorption processes involving atmospherically and geochemically important gases. The latter parts of this thesis were therefore focused on water vapor and carbon dioxide interactions with these FeOOH particles. These efforts showed how surface structure and speciation affect sorption loadings and configurations, as well as how water diffused into and through the akaganéite bulk. Hydrogen bonding is one of the most important forms of interactions between gas phase and minerals. It plays a crucial role in the formation of thin water films and in stabilizing surface (bi)carbonate species. The affinity of surface hydroxyl groups for water and carbon dioxide is strongly dependent on their abilities to form hydrogen bonds. These are controlled by coordination number and site accessibility/steric constraints. In agreement with the aforementioned ligand-exchange studies, surfaces dominated by singly coordinated groups have stronger ability to accumulate water layers than the ones terminated by groups of larger coordination number. Collectively, these efforts consolidate further the concept for structure-controlled reactivities in iron oxyhydroxides, and pave the way for new studies along such lines.

The great tunability of structure and electronic properties of π-conjugated organic molecules/polymers combined with other advantages such as light weight and flexibility etc., have made organic-based electronics the focus of an exciting still-growing field of physics and chemistry for more than half a century. The application of organic electronics has led to the appearance of wide range of organic electronic devices mainly including organic light emitting diodes (OLED), organic field effect transistors (OFET) and organic solar cells (OSC). The application of the organic electronic devices mainly is limited by two dominant parameters, i.e., their performance and stability. Up to date, OLED has been successfully commercialized in the market while the OSC are still on the way to commercialization hindered by low efficiency and inferior stability. Understanding the energy levels of organic materials and energy level alignment of the devices is crucial to control the efficiency and stability of the OSC. In this thesis, energy levels measured by different methods are studied to explore their relationship with device properties, and the strategies on how to design efficient and stable OSC based on energy level diagrams are provided. Cyclic Voltammetry (CV) is a traditional and widely used method to probe the energy levels of organic materials, although there is little consensus on how to relate the oxidation/reduction potential ((Eox/Ered) to the vacuum level. Ultraviolet Photoelectron Spectroscopy (UPS) can be used to directly detect vertical ionization potential (IP) of organic materials. In this thesis, a linear relationship of IP and Eox was found, with a slope equal to unity. The relationship provides for easy conversion of values obtained by the two techniques, enabling complementarily use in designing and fabricating efficient and stable OSC. A popular rule of thumb is that the offset between the LUMO levels of donor and acceptor should be 0.3 eV, according to which a binary solar cell with the minimum voltage losses around 0.49 V was designed here. Introduction of the ternary blend as active layer is an efficient way to improve both efficiency and stability of the OSC. Based on our studied energy-level diagram within the integer charge transfer (ICT) model, we designed ternary solar cells with enhanced open circuit voltage for the first time and improved thermal stability compared to reference binary ones. The ternary solar cell with minimum voltage losses was developed by combining two donor materials with same ionization potential and positive ICT energy while featuring complementary optical absorption. Furthermore, the fullerene acceptor was chosen so that the energy of the positive ICT state of the two donor polymers is equal to the energy of negative ICT state of the fullerene, which can enhance dissociation of all polymer donor and fullerene acceptor excitons and suppress bimolecular and trap-assistant recombination. Rapid development of non-fullerene acceptors in the last two years affords more recipes of designing both efficient and stabile OSC. We show in this thesis how non-fullerene acceptors successfully can be used to design ternary solar cells with both enhanced efficiency and thermal stability. Besides improving the efficiency of the devices, understanding of the stability and degradation mechanism is another key issue. The degradation of conjugated molecules/polymers often follow many complicated pathways and at the same time many factors for degradation are coupled with each other. Therefore, the degradation of non-fullerene acceptors was investigated in darkness by photoelectron spectroscopy in this thesis with the in-situ method of controlling exposure of O2 and water vapor separately.

This thesis presents the results of computer simulation studies of the structure, dynamics, and deformation of cross-linked polymer gels. Obtaining a fundamental understanding of the interrelation between the detailed structure and the properties of polymer gels is a challenge and a key issue towards designing materials for specific purposes. A new off-lattice method for constructing a closed network is presented that is free from defects, such as looping chains and dangling ends. Using these model networks in Brownian dynamics simulations, I show results for the structure and dynamics of bulk gels and describe a novel approach using spherical boundary conditions as an alternative to the periodic boundary conditions commonly used in simulations. This algorithm was also applied for simulating the diffusion of tracer particles within a static and dynamic network, to illustrate the quantitative difference and importance of including network mobility for large particles, as dynamic chains facilitate the escape of particles that become entrapped. I further investigate two technologically relevant properties of polymer gels: their stimuli-responsive behaviour and their mechanical properties. The collapse of core-shell nanogels was studied for a range of parameters, including the cross-linking degree and shell thickness. Two distinct regimes of gel collapse could be observed, with a rapid formation of small clusters followed by a coarsening stage. It is shown that in some cases, a collapsing shell may lead to an inversion of the core-shell particle which exposes the core polymer chains to the environment. This thesis also explores the deformation of bimodal gels consisting of both short and long chains, subject to uniaxial elongation, with the aim to understand the role of both network composition as well as structural heterogeneity on the mechanical response and the reinforcement mechanism of these materials. It is shown that a bimodal molecular weight distribution alone is sufficient to strongly alter the mechanical properties of networks compared to the corresponding unimodal networks with the same number-average chain length. Furthermore, it is shown that heterogeneities in the form of high-density short-chain clusters affect the mechanical properties relative to a homogeneous network, primarily by providing extensibility.

The thesis presents work regarding amphiphilic molecules associated in aqueous solution or at the liquid/solid interface. Two main topics are included: the temperature-dependent behavior of micelles and the adsorption of dispersants on carbon nanotube (CNT) surfaces. Various NMR methods were used to analyze those systems, such as chemical shift detection, spectral intensity measurements, spin relaxation and, in particular, self-diffusion experiments. Besides this, small angle X-ray scattering (SAXS) was also applied for structural characterization.   A particular form of phase transition, core freezing, was detected as a function of temperature in micelles composed by a single sort of Brij-type surfactants. In mixed micelles, that phase transition still occurs accompanied by a reversible segregation of different surfactants into distinct aggregates. Adding a hydrophobic solubilizate shifts the core freezing point to a lower temperature. Upon lowering the temperature to the core freezing point, the solubilizate is released. The temperature course of the release curves with different initial solubilizate loadings is rationalized in terms of a temperature-dependent loading capacity.   The behavior of amphiphilic dispersant molecules in aqueous dispersions of carbon nanotubes (CNTs) has been investigated with a Pluronic-type block copolymer as frequent model dispersant. Detailed dispersion curves were recorded and the distribution of the dispersant among different available environments was analyzed. The amount of dispersed CNT was shown to be defined by a complex interplay of several factors during the dispersion process such as dispersant concentration, sonication time, centrifugation and CNT loading. In the dispersion process, high amphiphilic concentration is required because the pristine CNT surfaces made available by sonication must be rapidly covered by dispersants to avoid their re-attachment. In the prepared dispersions, the competitive adsorption of possible dispersants was investigated that provided information about the relative strength of the interaction of those with the nanotube surfaces. Anionic surfactants were found to have a strong tendency to replace Pluronics, which indicates a strong binding of those surfactants.   CNTs were dispersed in an epoxy resin to prepare nanotube-polymer composites. The molecular mobility of epoxy was investigated and the results demonstrated the presence of loosely associated CNT aggregates within which the molecular transport of epoxy is slow because of strong attractive intermolecular interactions between epoxy and the CNT surface. The rheological behavior is dominated by aggregate-aggregate jamming. / <p>QC 20180103</p>

Organic electrode materials represent an intriguing alternative to their inorganic counterparts due to their sustainable and environmental-friendly properties. Their plastic character allows for the realization of light-weight, versatile and disposable devices for energy storage. Conducting redox polymers (CRPs) are one type of the organic electrode materials involved, which consist of a π-conjugated polymer backbone and covalently attached redox units, the so-called pendant. The polymer backbone can provide conductivity while it is oxidized or reduced (i. e., p- or n-doped) and the concurrent redox chemistry of the pendant provides charge capacity. The combination of these two components enables CRPs to provide both high charge capacity and high power capability. This dyad polymeric framework provides a solution to the two main problems associated with organic electrode materials based on small molecules: the dissolution of the active material in the electrolyte, and the sluggish charge transport within the material. This thesis introduces a general synthetic strategy to obtain the monomeric CRPs building blocks, followed by electrochemical polymerization to afford the active CRPs material. The choice of pendant and of polymer backbone depends on the potential match between these two components, i.e. the redox reaction of the pendant and the doping of backbone occurring within the same potential region. In the thesis, terephthalate and polythiophene were selected as the pendant and polymer backbone respectively, to get access to low potential CRPs. It was found that the presence of a non-conjugated linker between polymer backbone and pendant is essential for the polymerizability of the monomers as well as for the preservation of individual redox activities. The resulting CRPs exhibited fast charge transport within the polymer film and low activation barriers for charge propagation. These low potential CRPs were designed as the anode materials for energy storage applications. The combination of redox active pendant as charge carrier and a conductive polymer backbone reveals new insights into the requirements of organic matter based electrical energy storage materials.