This thesis investigates the structural, energetic, and electronic properties of two-dimensional (2D) materials, focusing on graphene, hexagonal boron nitride (hBN), transition metal dichalcogenides (TMDCs), and arsenic phosphide (AsP) bilayers, using dispersion-corrected density functional theory (DFT) and random Phase Approximation (RPA). Central to our analysis is the use of dispersion-corrected DFT methods, particularly the SCAN-rVV10 and PBE-rVV10L functionals, to accurately predict interlayer distances, interaction energies, and electronic properties. We assess these properties across a wide range of 2D materials in both homogeneous and heterostructured forms. This thesis demonstrates the effectiveness of standard DFT methods in predicting intralayer properties like bond lengths and lattice constants. However, it is the advanced London dispersion-corrected functionals, such as SCAN-rVV10, that are particularly effective in detailing interlayer distances and interactions. These interlayer phenomena are crucial for accurate material characterization and application. For instance, in homogeneous and heterostructured layered systems, SCAN-rVV10 accurately predicts interlayer distances and interaction energetics, aligning closely with experimental and higher-level theoretical RPA results. Moreover, in studying binding behavior, particularly for {Mo,Ti}S2 nanostructures interacting with organic molecules, we illustrate how molecular orientation and surface structure influence binding characteristics. This research emphasizes that molecule interactions at edge and basal plane sites are crucial for controlling the shape and growth of these nanostructures. Molecules often bind more strongly to edge sites, promoting edge passivation and vertical stacking, while basal plane interactions, especially with thiophene, favor lateral growth. In conclusion, this thesis not only advances our understanding of the fundamental properties of 2D materials but also provides crucial insights into the accuracy of DFT methods in predicting these properties. By identifying the strengths and limitations of different dispersion-corrected DFT methods, we open the way for more accurate computational research and practical applications of these materials. This comprehensive analysis bridges theoretical predictions with potential industrial applications, underscoring the transformative impact of 2D materials in science and technology.

A new mesoporous MOF, Zn4O(bpdc)(btctb)4/3 (DUT-32), containing linear ditopic (bpdc2−; 4,4′-biphenylenedicarboxylic acid) and tritopic (btctb3−; 4,4′,4′′-[benzene-1,3,5-triyltris(carbonylimino)]tris-benzoate) linkers, was synthesised. The highly porous solid has a total pore volume of 3.16 cm3 g−1 and a specific BET surface area of 6411 m2 g−1, adding this compound to the top ten porous materials with the highest BET surface area.

Hierarchical Kroll-carbons (KCs) with combined micro- and mesopore systems are prepared from silica and alumina templates by a reductive carbochlorination reaction of fumed silica and alumina nanoparticles inside a dense carbon matrix. The resulting KCs offer specific surface areas close to 2000 m2 g−1 and total pore volumes exceeding 3 cm3 g−1, resulting from their hierarchical pore structure. High micropore volumes of 0.39 cm3 g−1 are achieved in alumina-based KCs due to the enhanced carbon etching reaction being mainly responsible for the evolution of porosity. Mesopore sizes are uniform and precisely controllable over a wide range by the template particle dimensions. The possibility of directly recycling the process exhaust gases for the template synthesis and the use of renewable carbohydrates as the carbon source lead to a scalable and efficient alternative to classical hard- and soft templating approaches for the production of mesoporous and hierarchical carbon materials. Silica- and alumina-based Kroll-carbons are versatile electrode materials in electrochemical double-layer capacitors (EDLCs). Specific capacitances of up to 135 F g−1 in an aqueous electrolyte (1 M sulfuric acid) and 174 F g−1 in ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate) are achieved when measured in a symmetric cell configuration up to voltages of 0.6 and 2.5 V, respectively. 90% of the capacitance can be utilized at high current densities (20 A g−1) and room temperature rendering Kroll-carbons as attractive materials for EDLC electrodes resulting in high capacities and high rate performance due to the combined presence of micro- and mesopores.

Carbide-derived carbon Monoliths (CDC-Ms) containing a multimodal arrangement with high volumes of micro- meso- and macropores are prepared by direct nanocasting of silica monoliths with polycarbosilane precursors. CDC-Ms show well-defined pore structures along with specific surface areas of more than 2600 m2 g−1 and overall pore volumes as high as 3.14 cm3 g−1. They exhibit advanced gas filtration properties compared to purely microporous materials due to enhanced storage capacities and kinetics as demonstrated by thermal response measurements based on InfraSORP technology.

Non-ordered porous networks, so-called aerogels, can be achieved by the 3D assembly of quantum dots (QDs). These materials are well suited for photonic applications, however a certain quenching of the photoluminescence (PL) intensity is observed in these structures. This PL quenching is mainly attributed to the energy transfer mechanisms that result from the close contact of the nanoparticles in the network. Here, we demonstrate the formation of a novel aerogel material with non-quenching PL behaviour by non-classical, reversible gel formation from tetrazole capped silica encapsulated QDs. Monitoring of the gelation/degelation by optical spectroscopy showed that the optical properties of the nanocrystals could be preserved in the 3D network since no spectral shifts and lifetime shortening, which can be attributed to the coupling between QDs, are observed in the gels as compared to the original colloidal solutions. In comparison with other QD-silica monoliths, QDs in our gels are homogeneously distributed with a distinct and controllable distance. In addition we show that the silica shell is porous and allows metal ions to pass through the shell and interact with the QD core causing detectable changes of the emission properties. We further show the applicability of this gelation method to other QD materials which sets the stage for facile preparation of a variety of mixed gel structures.

Neutral cyclometalated platinum(II) N-heterocyclic carbene complexes [Pt(C^C*)(O^O)] with C^C* ligands based on 1-phenyl-1,2,4-triazol-5-ylidene and 4-phenyl-1,2,4-triazol-5-ylidene, as well as acetylacetonato (O^O = acac) and 1,3-bis(2,4,6-trimethylphenyl)propan-1,3-dionato (O^O = mesacac) ancillary ligands were synthesized and characterized. All complexes are emissive at room temperature in a poly(methyl methacrylate) (PMMA) matrix with emission maxima in the blue region of the spectrum. High quantum efficiencies and short decay times were observed for all complexes with mesacac ancillary ligands. The sterically demanding mesityl groups of the mesacac ligand effectively prevent molecular stacking. The emission behavior of these emitters is in general independent of the position of the nitrogen in the backbone of the N-heterocyclic carbene (NHC) unit and a variety of substituents in 4-position of the phenyl unit, meta to the cyclometalating bond.

Chitosan is known for its hemostatic and antimicrobial properties and might be useful for temporary coating of removable dentures or intraoral splints to control bleeding after oral surgery or as a supportive treatment in denture stomatitis. This study investigated a new method to adhere chitosan to polymethyl methacrylate (PMMA) and polyethylene terephthalate (PET). There were 70 cylindrical specimens made from PMMA and 70 from PET (13 mm diameter, 6 mm thickness). The materials with ten specimens each were sandblasted at 2.8 or 4.0 bar with aluminum oxide 110 μm or/and aluminum oxide coated with silica. After sandblasting, all specimens were coated with a 2% or 4% acetic chitosan solution with a thickness of 1 mm. Then the specimens were dried for 120 min at 45 °C. The precipitated chitosan was neutralized with 1 mol NaOH. After neutralization, all specimens underwent abrasion tests using the tooth-brushing simulator with soft brushes (load 2N, 2 cycles/s, 32 °C, 3000 and 30,000 cycles). After each run, the specimen surfaces were analyzed for areas of remaining chitosan by digital planimetry under a light microscope. The best chitosan adhesion was found after sandblasting with aluminum oxide coated with silica (U-Test, p < 0.05) in both the PMMA and the PET groups. Hence, with relatively simple technology, a reliable bond of chitosan to PMMA and PET could be achieved.

This review aims to highlight and comprehensively summarize recent developments in the field of mixed-coordinate phosphorus chemistry. Particular attention is focused on the synthetic approaches to compounds containing at least two directly bonded phosphorus atoms in different coordination environments and their unexpected properties that are derived from spectroscopic and crystallographic data. Novel substance classes are discussed in order to supplement previous reviews about mixed-coordinate phosphorus compounds.

We present the synthesis and structural characterization of novel ruthenium complexes containing C^C* cyclometalated N-heterocyclic carbene ligands, η6-arene (p-cymene) ligands and one bridging chlorine ion. Complexes of the general formula [Ru(p-cymene)(C^C*)Cl] were prepared via a one-pot synthesis using in situ transmetalation from the correspondent silver NHC complexes. These complexes react with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBArF4) to form dinuclear complexes of the general structure [Ru(p-cymene)(C^C*)-μ-Cl-(p-cymene)(C^C*)Ru]+[BArF4]−. Solid-state structures confirm that the pseudo-tetrahedral coordination around the metal center with the η6-ligand aligned perpendicularly to the C^C* ligand and the i-Pr group “atop” is retained in the bimetallic complexes.

A new approach for the fine tuning of flexibility in MOFs, involving functionalization of the secondary building unit, is presented. The 'gate pressure' MOF [Zn3(bpydc)2(HCOO)2] was used as a model material and SBU functionalization was performed by using monocarboxylic acids such as acetic, benzoic or cinnamic acids instead of formic acid in the synthesis. The resulting materials are isomorphous to [Zn3(bpydc)2(HCOO)2] in the 'as made' form, but show different structural dynamics during the guest removal. The activated materials have entirely different properties in the nitrogen physisorption experiments clearly showing the tunability of the gate pressure, at which the structural transformation occurs, by using monocarboxylic acids with varying backbone structure in the synthesis. Thus, increasing the number of carbon atoms in the backbone leads to the decreasing gate pressure required to initiate the structural transition. Moreover, in situ adsorption/PXRD data suggest differences in the mechanism of the structural transformations: from 'gate opening' in the case of formic acid to 'breathing' if benzoic acid is used.