Structure, organization and dynamics of functional supramolecular materials studied by solid-state NMR

Functional materials have great importance due to their many important applications. The characterization of supramolecular architectures which are held together by non-covalent interactions is of most importance to understand their properties. Solid-state NMR methods have recently been proven to be able to unravel such structure-property relations with the help of fast magic-angle spinning and advanced pulse sequences. The aim of the current work is to understand the structure and dynamics of functional supramolecular materials which are potentially important for fuel-cell (proton conducting membrane materials) and solar-cell or plastic-electronic applications (photo-reactive aromatic materials). In particular, hydrogen-bonding networks, local proton mobility, molecular packing arrangements, and local dynamics will be studied by the use of advanced solid-state NMR methods. The first class of materials studied in this work is proton conducting polymers which also form hydrogen-bonding network. Different materials, which are prepared for high 1H conduction by different approaches are studied: PAA-P4VP, PVPA-ABPBI, Tz5Si, and Triazole-functional systems. The materials are examples of the following major groups; - Homopolymers with specific functional groups (Triazole functional polysiloxanes). - Acid-base polymer blends approach (PAA-P4VP, PVPA-ABPBI). - Acid-base copolymer approach (Triazole-PVPA). - Acid doped polymers (Triazole functional polymer doped with H3PO4). Perylenebisimide (PBI) derivatives, a second type of important functional supramolecular materials with potent applications in plastic electronics, were also investigated by means of solid-state NMR. The preparation of conducting nanoscopic fibers based on the self-assembling functional units is an appealing aim as they may be incorporated in molecular electronic devices. In this category, perylene derivatives have attracted great attention due to their high charge carrier mobility. A detailed knowledge about their supramolecular structure and molecular dynamics is crucial for the understanding of their electronic properties. The aim is to understand the structure, dynamics and packing arrangements which lead to high electron conductivity in PBI derivatives.

Simulations of charge transport in organic compounds

To aid the design of organic semiconductors, we study the charge transport properties of organic liquid crystals, i.e. hexabenzocoronene and carbazole macrocycle, and single crystals, i.e. rubrene, indolocarbazole and benzothiophene derivatives (BTBT, BBBT). The aim is to find structure-property relationships linking the chemical structure as well as the morphology with the bulk charge carrier mobility of the compounds. To this end, molecular dynamics (MD) simulations are performed yielding realistic equilibrated morphologies. Partial charges and molecular orbitals are calculated based on single molecules in vacuum using quantum chemical methods. The molecular orbitals are then mapped onto the molecular positions and orientations, which allows calculation of the transfer integrals between nearest neighbors using the molecular orbital overlap method. Thus we obtain realistic transfer integral distributions and their autocorrelations. In case of organic crystals the differences between two descriptions of charge transport, namely semi-classical dynamics (SCD) in the small polaron limit and kinetic Monte Carlo (KMC) based on Marcus rates, are studied. The liquid crystals are investigated solely in the hopping limit. To simulate the charge dynamics using KMC, the centers of mass of the molecules are mapped onto lattice sites and the transfer integrals are used to compute the hopping rates. In the small polaron limit, where the electronic wave function is spread over a limited number of neighboring molecules, the Schroedinger equation is solved numerically using a semi-classical approach. The results are compared for the different compounds and methods and, where available, with experimental data. The carbazole macrocycles form columnar structures arranged on a hexagonal lattice with side chains facing inwards, so columns can closely approach each other allowing inter-columnar and thus three-dimensional transport. When taking only intra-columnar transport into account, the mobility is orders of magnitude lower than in the three-dimensional case. BTBT is a promising material for solution-processed organic field-effect transistors. We are able to show that, on the time-scales of charge transport, static disorder due to slow side chain motions is the main factor determining the mobility. The resulting broad transfer integral distributions modify the connectivity of the system but sufficiently many fast percolation paths remain for the charges. Rubrene, indolocarbazole and BBBT are examples of crystals without significant static disorder. The high mobility of rubrene is explained by two main features: first, the shifted cofacial alignment of its molecules, and second, the high center of mass vibrational frequency. In comparsion to SCD, only KMC based on Marcus rates is capable of describing neighbors with low coupling and of taking static disorder into account three-dimensionally. Thus it is the method of choice for crystalline systems dominated by static disorder. However, it is inappropriate for the case of strong coupling and underestimates the mobility of well-ordered crystals. SCD, despite its one-dimensionality, is valuable for crystals with strong coupling and little disorder. It also allows correct treatment of dynamical effects, such as intermolecular vibrations of the molecules. Rate equations are incapable of this, because simulations are performed on static snapshots. We have thus shown strengths and weaknesses of two state of the art models used to study charge transport in organic compounds, partially developed a program to compute and visualize transfer integral distributions and other charge transport properties, and found structure-mobility relations for several promising organic semiconductors.

Structure formation as studied by EPR spectroscopy: From simple solutions to nanoparticles

In this thesis, three nitroxide based ionic systems were used to investigate structure and dynamics of their respective solutions in mixed solvents by means of electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) spectroscopy at X- and W-band (9.5 and 94.5 GHz, respectively). rnFirst, the solvation of the inorganic radical Fremy’s salt (K2ON(SO3)2) in isotope substituted binary solvent mixtures (methanol/water) was investigated by means of high-field (W-band) pulse ENDOR spectroscopy and molecular dynamics (MD) simulations. From the analysis of orientation-selective 1H and 2H ENDOR spectra the principal components of the hyperfine coupling (hfc) tensor for chemically different protons (alcoholic methyl vs. exchangeable protons) were obtained. The methyl protons of the organic solvent approach with a mean distance of 3.5 Å perpendicular to the approximate plane spanned by ON(S)2 of the probe molecule. Exchangeable protons were found to be distributed isotropically, approaching closest to Fremy’s salt from the hydrogen-bonded network around the sulfonate groups. The distribution of exchangeable and methyl protons as found in MD simulations is in full agreement with the ENDOR results. The solvation was found to be similar for the studied solvent ratios between 1:2.3 and 2.3:1 and dominated by an interplay of H-bond (electrostatic) interactions and steric considerations with the NO group merely involved into H-bonds.rnFurther, the conformation of spin labeled poly(diallyldimethylammonium chloride) (PDADMAC) solutions in aqueous alcohol (methanol, ethanol, n-propanol, ethylene glycol, glycerol) mixtures in dependence of divalent sodium sulfate was investigated with double electron-electron resonance (DEER) spectroscopy. The DEER data was analyzed using the worm-like chain model which suggests that in organic-water solvent mixtures the polymer backbones are preferentially solvated by the organic solvent. We found a less serve impact on conformational changes due to salt than usually predicted in polyelectrolyte theory which stresses the importance of a delicate balance of hydrophobic and electrostatic interactions, in particular in the presence of organic solvents.rnFinally, the structure and dynamics of miniemulsions and polymerdispersions prepared with anionic surfactants, that were partially replaced by a spin labeled fatty acid in presence and absence of a lanthanide beta-diketonate complex was characterized by CW EPR spectroscopy. Such miniemulsions form multilayers with the surfactant head group bound to the lanthanide ion. Beta-diketonates were formerly used as NMR shift reagents and nowadays find application as luminescent materials in OLEDs and LCDs and as contrast agent in MRT. The embedding of the complex into a polymer matrix results in an easy processable material. It was found that the structure formation takes place in miniemulsion and is preserved during polymerization. For surfactants with carboxyl-head group a higher order of the alkyl chains and less lateral diffusion is found than for sulfat-head groups, suggesting a more uniform and stronger coordination to the metal ion. The stability of these bilayers depends on the temperature and the used surfactant which should be considered for the used polymerization temperature if a maximum output of the structured regions is wished.

Charge transport in amorphous organic semiconductors

Organic semiconductors with the unique combination of electronic and mechanical properties may offer cost-effective ways of realizing many electronic applications, e.g. large-area flexible displays, printed integrated circuits and plastic solar cells. In order to facilitate the rational compound design of organic semiconductors, it is essential to understand relevant physical properties e.g. charge transport. This, however, is not straightforward, since physical models operating on different time and length scales need to be combined. First, the material morphology has to be known at an atomistic scale. For this atomistic molecular dynamics simulations can be employed, provided that an atomistic force field is available. Otherwise it has to be developed based on the existing force fields and first principle calculations. However, atomistic simulations are typically limited to the nanometer length- and nanosecond time-scales. To overcome these limitations, systematic coarse-graining techniques can be used. In the first part of this thesis, it is demonstrated how a force field can be parameterized for a typical organic molecule. Then different coarse-graining approaches are introduced together with the analysis of their advantages and problems. When atomistic morphology is available, charge transport can be studied by combining the high-temperature Marcus theory with kinetic Monte Carlo simulations. The approach is applied to the hole transport in amorphous films of tris(8-hydroxyquinoline)aluminium (Alq3). First the influence of the force field parameters and the corresponding morphological changes on charge transport is studied. It is shown that the energetic disorder plays an important role for amorphous Alq3, defining charge carrier dynamics. Its spatial correlations govern the Poole-Frenkel behavior of the charge carrier mobility. It is found that hole transport is dispersive for system sizes accessible to simulations, meaning that calculated mobilities depend strongly on the system size. A method for extrapolating calculated mobilities to the infinite system size is proposed, allowing direct comparison of simulation results and time-of-flight experiments. The extracted value of the nondispersive hole mobility and its electric field dependence for amorphous Alq3 agree well with the experimental results.

Coarse-graining and quantum-classical adaptive coupling in soft matter

Die vorliegende Arbeit untersucht den Zusammenhang zwischen Skalen in Systemen weicher Materie, der für Multiskalen-Simulationen eine wichtige Rolle spielt. Zu diesem Zweck wurde eine Methode entwickelt, die die Approximation der Separierbarkeit von Variablen für die Molekulardynamik und ähnliche Anwendungen bewertet. Der zweite und größere Teil dieser Arbeit beschäftigt sich mit der konzeptionellen und technischen Erweiterung des Adaptive Resolution Scheme'' (AdResS), einer Methode zur gleichzeitigen Simulation von Systemen mit mehreren Auflösungsebenen. Diese Methode wurde auf Systeme erweitert, in denen klassische und quantenmechanische Effekte eine Rolle spielen.rnrnDie oben genannte erste Methode benötigt nur die analytische Form der Potentiale, wie sie die meisten Molekulardynamik-Programme zur Verfügung stellen. Die Anwendung der Methode auf ein spezielles Problem gibt bei erfolgreichem Ausgang einen numerischen Hinweis auf die Gültigkeit der Variablenseparation. Bei nicht erfolgreichem Ausgang garantiert sie, dass keine Separation der Variablen möglich ist. Die Methode wird exemplarisch auf ein zweiatomiges Molekül auf einer Oberfläche und für die zweidimensionale Version des Rotational Isomer State (RIS) Modells einer Polymerkette angewandt.rnrnDer zweite Teil der Arbeit behandelt die Entwicklung eines Algorithmus zur adaptiven Simulation von Systemen, in denen Quanteneffekte berücksichtigt werden. Die Quantennatur von Atomen wird dabei in der Pfadintegral-Methode durch einen klassischen Polymerring repräsentiert. Die adaptive Pfadintegral-Methode wird zunächst für einatomige Flüssigkeiten und tetraedrische Moleküle unter normalen thermodynamischen Bedingungen getestet. Schließlich wird die Stabilität der Methode durch ihre Anwendung auf flüssigen para-Wasserstoff bei niedrigen Temperaturen geprüft.