Chemical synthesis of materials is facing enormous challenges at the present time. The necessary transition toward more sustainable economic processes requires new materials as well as optimized production of well-established materials. However, inorganic materials (e.g., ceramics or alloys) are typically produced industrially by high-temperature processes at up to 2000 °C. A relatively new approach for inorganic synthesis is based on so-called ionic liquids. Ionic liquids (ILs) — often defined as salts with melting points below 100 °C[1] — are usually composed of sterically demanding organic cations and (often) polyatomic anions, which can be selected in order to tune the properties of the IL. Owing to the distinctive physicochemical properties of ILs (e.g., wide liquidus range, high redox and thermal stability, (usually) negligible vapor pressure, tunable polarity), they have gained interest for a wide range of applications. Among the numerous inorganic materials accessible in ILs have been remarkable examples, especially in main-group element chemistry. For instance, a new metastable modification of germanium in the clathrate-II structure[2] or the largest known naked, main-group element cluster [Sn36Ge24Se132]24– (“Zeoball”).[3] The introduction of Lewis-acidic ILs has enhanced the convenience of polycation syntheses and enabled substitution of carcinogenic or toxic substances like benzene, SO2, or AsF5.[4] A considerable number of polycations of group 15 or 16 elements has been synthesized in ILs. The utilization of an IL as reaction medium can be decisive for the composition, structure, and physical properties of the (polycationic) reaction product.[5] In order to broaden the knowledge on synthesis techniques for inorganic materials near ambient temperature based on ILs, this thesis aimed at two goals: • Explorative synthesis of new inorganic compounds in ILs • Elucidating the influence of ILs on product formation For these two goals, metal-rich (polycationic) compounds of group 15 were chosen as promising chemical system, owing to the effectiveness of alkylimidazolium-based Lewis-acidic ILs for the synthesis of this class of compounds. A variety of new polycationic compounds has been successfully synthesized in Lewis-acidic ILs based on 1-n-butyl-3-methylimidazolium (or 1-ethy-3-methylimidazolium) halides and halogenido-aluminates. Determination of the crystal structures by single-crystal X-ray diffraction enabled analysis of their bonding situation supported by quantum-chemical calculations. In general, the employed ILs enabled syntheses with a high selectivity for the yielded polycation. Depending on the investigated chemical system, the following parameters were pinpointed to have significant influence: • Choice of starting materials • Choice of cation as well as anion of the IL • Reaction temperature • Concentration of starting materials in the IL The investigations were supported by NMR spectroscopy, which led to the discovery of nanoparticles of red phosphorus. This finding may stimulate the development of an easily accessible, reactive form of phosphorus without the hazardous drawbacks of the white allotrope. In addition, in situ NMR measurements in ILs were proven a viable option for mechanistic investigations. Conventional solid-state reaction as well as ionothermal syntheses yielded the new layered compounds M2Bi2S3(AlCl4)2 (M = Cu, Ag), which can be interpreted as Bi2S3 molecules embedded in MAlCl4 salts. The choice of starting materials was found to have a crucial influence on the crystallized polytype. Omitting the IL hindered the formation of crystals suitable for single-crystal structure determination. The three new main-group element heteropolycations [Bi6Te4Br2]4+, [Bi3S4AlCl]3+, and [Sb13Se16]7+ as well as known [Bi4Te4]4+ has been synthesized under ionothermal conditions. The Lewis-acidic ILs proved to be exceptional solvents for elements and their halides, and likewise for Bi2S3 and Bi2Te3. Hence, these solvents are not only advantageous reaction media for pnictogen and chalcogen chemistry but also potential (selective but expensive) ore-processing agents. These excellent solvent capabilities extend to complex ternary compounds including heavy transition metals such as Bi16PdCl22 and elemental platinum. This gave rise to the synthesis of metal-rich salts containing [Bi10]4+ antiprisms with an endohedral palladium or, for the first time, platinum atom. Furthermore, the filled bismuth polycation [Rh@Bi9]4+ or the complex cluster [Rh2Bi12]4+ could be obtained from dissolution and conversion of Bi12−xRhX13–x (X = Cl, Br) depending on the employed IL. Real-space bonding analysis revealed that [Rh2Bi12]4+ acquires a unique standing between dative bonding by bismuth polyions and mixed clusters following Wade-Mingos rules. References [1] J. S. Wilkes, P. Wasserscheid, T. Welton, in Ionic Liquids in Synthesis (Eds.: P. Wasserscheid, T. Welton), Wiley-VCH Verlag GmbH & Co. KGaA, 2007, pp. 1–6. [2] A. M. Guloy, R. Ramlau, Z. Tang, W. Schnelle, M. Baitinger, Y. Grin, Nature 2006, 443, 320–323. [3] Y. Lin, W. Massa, S. Dehnen, J. Am. Chem. Soc. 2012, 134, 4497–4500. [4] E. Ahmed, D. Köhler, M. Ruck, Z. Anorg. Allg. Chem. 2009, 635, 297–300. [5] E. Ahmed, J. Beck, J. Daniels, T. Doert, S. J. Eck, A. Heerwig, A. Isaeva, S. Lidin, M. Ruck, W. Schnelle, et al., Angew. Chem. 2012, 124, 8230–8233; Angew. Chem. Int. Ed. 2012, 51, 8106–8109.

A NMR study of the structure-dynamics relationships in heterogeneous materials is presented. In the first part, transport in soft-matter systems is studied using the pulsed field gradient NMR technique (PFG NMR). The molecular crowding effect in biological matter has been addressed using polymer solutions as model systems. By performing ensemble-based diffusion studies, the earlier obtained data on anomalous diffusion have been complemented. The transition to normal diffusion on a larger time scale has been shown. Taking advantages of the NMR approach, transport properties of microemulsions consisting of micellar colloids dissolved in liquid crystals have been investigated. The self-diffusivities measured under equilibrium conditions have shown weak correlations with microscopic ordering and macroscopic phase transitions occurring in the systems under study. The formation of micelles is shown to be decisive for macroscopic separation at the isotropic-nematic transition. The second part of the thesis covers heterogeneous effects in diffusion for fluids in porous solids, as probed using a combination of NMR diffusometry and structure characterization methods. Ionic liquids have been investigated, revealing a complex behavior under confinement. The attempts to correlate the observed characteristics of the ionic liquids with their internal chemical structure were undertaken. Finally, the series of nanoporous glasses with tunable pore structure characteristics were studied. Strong correlations between their structure and the preparation conditions as well as between the resulting transport properties have been shown.

Chemical synthesis of materials is facing enormous challenges at the present time. The necessary transition toward more sustainable economic processes requires new materials as well as optimized production of well-established materials. However, inorganic materials (e.g., ceramics or alloys) are typically produced industrially by high-temperature processes at up to 2000 °C. A relatively new approach for inorganic synthesis is based on so-called ionic liquids. Ionic liquids (ILs) — often defined as salts with melting points below 100 °C[1] — are usually composed of sterically demanding organic cations and (often) polyatomic anions, which can be selected in order to tune the properties of the IL. Owing to the distinctive physicochemical properties of ILs (e.g., wide liquidus range, high redox and thermal stability, (usually) negligible vapor pressure, tunable polarity), they have gained interest for a wide range of applications. Among the numerous inorganic materials accessible in ILs have been remarkable examples, especially in main-group element chemistry. For instance, a new metastable modification of germanium in the clathrate-II structure[2] or the largest known naked, main-group element cluster [Sn36Ge24Se132]24– (“Zeoball”).[3] The introduction of Lewis-acidic ILs has enhanced the convenience of polycation syntheses and enabled substitution of carcinogenic or toxic substances like benzene, SO2, or AsF5.[4] A considerable number of polycations of group 15 or 16 elements has been synthesized in ILs. The utilization of an IL as reaction medium can be decisive for the composition, structure, and physical properties of the (polycationic) reaction product.[5] In order to broaden the knowledge on synthesis techniques for inorganic materials near ambient temperature based on ILs, this thesis aimed at two goals: • Explorative synthesis of new inorganic compounds in ILs • Elucidating the influence of ILs on product formation For these two goals, metal-rich (polycationic) compounds of group 15 were chosen as promising chemical system, owing to the effectiveness of alkylimidazolium-based Lewis-acidic ILs for the synthesis of this class of compounds. A variety of new polycationic compounds has been successfully synthesized in Lewis-acidic ILs based on 1-n-butyl-3-methylimidazolium (or 1-ethy-3-methylimidazolium) halides and halogenido-aluminates. Determination of the crystal structures by single-crystal X-ray diffraction enabled analysis of their bonding situation supported by quantum-chemical calculations. In general, the employed ILs enabled syntheses with a high selectivity for the yielded polycation. Depending on the investigated chemical system, the following parameters were pinpointed to have significant influence: • Choice of starting materials • Choice of cation as well as anion of the IL • Reaction temperature • Concentration of starting materials in the IL The investigations were supported by NMR spectroscopy, which led to the discovery of nanoparticles of red phosphorus. This finding may stimulate the development of an easily accessible, reactive form of phosphorus without the hazardous drawbacks of the white allotrope. In addition, in situ NMR measurements in ILs were proven a viable option for mechanistic investigations. Conventional solid-state reaction as well as ionothermal syntheses yielded the new layered compounds M2Bi2S3(AlCl4)2 (M = Cu, Ag), which can be interpreted as Bi2S3 molecules embedded in MAlCl4 salts. The choice of starting materials was found to have a crucial influence on the crystallized polytype. Omitting the IL hindered the formation of crystals suitable for single-crystal structure determination. The three new main-group element heteropolycations [Bi6Te4Br2]4+, [Bi3S4AlCl]3+, and [Sb13Se16]7+ as well as known [Bi4Te4]4+ has been synthesized under ionothermal conditions. The Lewis-acidic ILs proved to be exceptional solvents for elements and their halides, and likewise for Bi2S3 and Bi2Te3. Hence, these solvents are not only advantageous reaction media for pnictogen and chalcogen chemistry but also potential (selective but expensive) ore-processing agents. These excellent solvent capabilities extend to complex ternary compounds including heavy transition metals such as Bi16PdCl22 and elemental platinum. This gave rise to the synthesis of metal-rich salts containing [Bi10]4+ antiprisms with an endohedral palladium or, for the first time, platinum atom. Furthermore, the filled bismuth polycation [Rh@Bi9]4+ or the complex cluster [Rh2Bi12]4+ could be obtained from dissolution and conversion of Bi12−xRhX13–x (X = Cl, Br) depending on the employed IL. Real-space bonding analysis revealed that [Rh2Bi12]4+ acquires a unique standing between dative bonding by bismuth polyions and mixed clusters following Wade-Mingos rules. References [1] J. S. Wilkes, P. Wasserscheid, T. Welton, in Ionic Liquids in Synthesis (Eds.: P. Wasserscheid, T. Welton), Wiley-VCH Verlag GmbH & Co. KGaA, 2007, pp. 1–6. [2] A. M. Guloy, R. Ramlau, Z. Tang, W. Schnelle, M. Baitinger, Y. Grin, Nature 2006, 443, 320–323. [3] Y. Lin, W. Massa, S. Dehnen, J. Am. Chem. Soc. 2012, 134, 4497–4500. [4] E. Ahmed, D. Köhler, M. Ruck, Z. Anorg. Allg. Chem. 2009, 635, 297–300. [5] E. Ahmed, J. Beck, J. Daniels, T. Doert, S. J. Eck, A. Heerwig, A. Isaeva, S. Lidin, M. Ruck, W. Schnelle, et al., Angew. Chem. 2012, 124, 8230–8233; Angew. Chem. Int. Ed. 2012, 51, 8106–8109.

Hydraulic development engineers and tribology specialist still exert substantial effort, time and resources into finding a hydraulic fluid that would be near an ideal fluid. In addition to its basic physicochemical properties, it must meet a number of other requirements related to its practical use within hydraulic system and the materials used therein. Ionic Liquids, as novel lubricants, offer the solution in this regard. The paper gives an overview of the basic properties of selected and tested Ionic Liquids suitable for use as hydraulic fluids. The practically obtained data refer to the basic physico-chemical properties of Ionic Liquids and properties important for practical use within hydraulic system, e.g. compatibility with materials. The results are given in a comparison with common mineral oil based hydraulic oil.

Die vorliegende Arbeit befasst sich mit der Synthese phosphorhaltiger anorganischer Verbindungen in ionischen Flüssigkeiten (engl. ionic liquids, ILs) und legt einen Schwerpunkt auf die Untersuchung der grundlegenden mechanistischen Abläufe, insbesondere auf die Aktivierung von elementarem Phosphor in ILs. Durch die Kombination spektroskopischer und theoretischer Methoden wurde ausführlich das chemische Verhalten von Phosphorhalogeniden in halogenidhaltigen ILs analysiert. Es konnte gezeigt werden, dass nach der Auflösung von rotem Phosphor mit Iod ein Gleichgewicht in der Lösung vorliegt, welches zu der Bildung von Tetrachlorophosphat führt. Insgesamt weist der beobachtete, dynamische Koordinationsprozess der Liganden Ähnlichkeiten zu einer strukturellen Diffusion bzw. Grotthuss-Diffusion auf. Diese Mischungen könnten somit potenziell als kostengünstige Elektrolyte verwendet werden. In weiteren Untersuchungen gelang es, aus Cu und rotem Phosphor in halogenidhaltigen ILs reproduzierbar und in hoher Reinheit Cu3−xP (x = 0,05) zu synthetisieren. Die Optimierung der Reaktion ermöglichte dabei Ausbeuten von über 99 %. Während der Reaktion kommt es zu einer IL-induzierten nukleophilen Aktivierung des roten Phosphors, wodurch hochreaktive P4-Moleküle gebildet werden. Durch die direkte Verwendung von P4 in ILs konnte nachfolgend erstmals kupferarmes Cu3−xP (0,1 < x < 0,7) gezielt synthetisiert werden, ohne das phosphorreiche Nebenprodukte gebildet wurden. Die elektrochemische Charakterisierung unterschiedlicher Cu3−xP-Phasen als Anodenmaterial in Lithium-Ionen-Akkumulatoren zeigte, dass sich das chemische Verhalten gegen Li mit der Zusammensetzung des Materials ändert. Da sich kupferarmes Cu3−xP durch eine höhere Kapazität und kupferreiches Material durch eine bessere Zykelnstabilität auszeichnet, erlauben die Ergebnisse dieser Arbeit die weitere Optimierungen dieses Materials für den Einsatz in Akkumulatoren.:1. Motivation und Einleitung 1 1.1. Klassische Flussmittel in der Materialsynthese 2 1.2. Ionische Flüssigkeiten 4 1.2.1. Struktur und Eigenschaften 4 1.2.2. Anwendung in der Synthese von anorganischen Materialien 6 1.3. Reaktionen mit elementarem Phosphor in ionischen Flüssigkeiten 8 1.3.1. Struktur und Eigenschaften der Phosphormodifikationen 8 1.3.2. Synthetische Verwendung in ionischer Flüssigkeit 10 1.4. Zielstellung der Arbeit 11 2. Allgemeiner experimenteller Teil 12 2.1. Schutzgasatmosphäre 12 2.2. Verwendeten Chemikalien 12 2.2.1. Anorganische Ausgangsverbindungen 12 2.2.2. Ionische Flüssigkeiten 13 2.2.3. Lösungsmittel 14 2.2.4. Präparationsvorschriften 14 2.3. Charakterisierungsmethoden 15 2.3.1. Röntgenpulverdiffraktometrie 15 2.3.2. Einkristall-Röntgenstrukturanalyse 15 2.3.3. Rasterelektronenmikroskopie 15 2.3.4. Energiedispersive Röntgenspektroskopie 16 2.3.5. Elementaranalyse 16 2.3.6. Kernspinresonanzspektroskopie 17 2.3.7. Raman-Spektroskopie 17 2.3.8. Röntgenabsorptionsspektroskopie 18 2.3.9. Elektronenspinresonanz-Spektroskopie 18 2.3.10. Elektrische Transportmessungen 18 2.3.11. Elektrochemische Charakterisierung 19 2.3.12. Wärmekapazitätsmessungen 20 2.3.13. Quantenchemische Berechnungen 20 3. Untersuchungen zur Bildung von Phosphorhalogeniden aus rotem Phosphor 22 3.1. Einleitung 22 3.2. Experimenteller Teil 23 3.3. Reaktion von rotem Phosphor mit Iod in [BMIm]X (X = Cl, I) 24 3.4. Anionenaustausch von PX3 in [HMIm]X (X = Cl, Br, I) 25 3.4.1. Reaktion von rotem Phosphor mit Iod in [HMIm]X (X = Cl, Br, I) 25 3.4.2. Phosphortrihalogenid-Referenzsystem 26 3.5. Das molekulare Verhalten von PCl3 in [HMIm]Cl 30 3.6. Quantenchemische Rechnungen 33 3.6.1. Molekulardynamische Simulationen 33 3.6.2. Statische DFT-Rechnungen 38 3.6.3. Mechanismus des Halogenaustausches 40 3.7. Zusammenfassung 41 4. Die Synthese von Cu3−xP – ein Modellsystem zur Reaktionsanalyse 43 4.1. Einleitung 43 4.2. Darstellungsmethoden – eine Literaturübersicht 45 4.3. Synthese von Cu3−xP (x = 0,05) in ionischen Flüssigkeiten 47 4.3.1. Synthesevorschrift 47 4.3.2. Produktcharakterisierung 47 4.3.3. Die Stabilität der ionischen Flüssigkeiten unter Synthesebedingungen 49 4.3.4. Analyse des Cu3−xP-Homogenitätsbereiches 50 4.4. Synthese von Cu3−xP (0,1 < x < 0,7) in ionischen Flüssigkeiten 52 4.4.1. Synthesevorschrift 52 4.4.2. Produktcharakterisierung 53 4.4.3. Analyse des Cu3−xP-Homogenitätsbereiches 55 4.5. Mechanistische Untersuchungen zur Cu3−xP-Bildung in [P66614]Cl 57 4.5.1. Experimenteller Teil 57 4.5.2. Diffusionsexperimente mit rotem Phosphor 58 4.5.3. Aktivierung von rotem Phosphor in [P66614]Cl 59 4.5.4. Mechanistische Diskussion der Cu3−xP-Phasenbildung 61 4.6. Untersuchungen zur Optimierung der Phosphoraktivierung 63 4.6.1. Donor- und Akzeptoreigenschaften ionischer Flüssigkeiten 64 4.6.2. Experimenteller Teil 66 4.6.3. Ergebnisse und Diskussion 66 4.7. Anioneneinfluss auf die Cu3−xP-Phasenbildung 69 4.7.1. Experimenteller Teil 69 4.7.2. Ergebnisse und Diskussion 70 4.8. Temperaturabhängige Kristallstrukturanalyse von Cu3−xP 72 4.8.1. Kristallzüchtung 72 4.8.2. Ergebnisse und Diskussion 73 4.9. Physikalische Charakterisierung unterschiedlicher Cu3−xP-Phasen 77 4.9.1. Elektronische Transporteigenschaften 77 4.9.2. Elektrochemische Charakterisierung 79 4.10. Zusammenfassung 82 5. Hochschmelzende ionische Flüssigkeiten in der Synthese von CuP2 84 5.1. Einleitung 84 5.2. Synthesevorschrift 85 5.3. Ergebnisse und Diskussion 85 5.4. Zusammenfassung 88 6. Fazit und Ausblick 89 A. Anhang 91 A.1. Röntgenpulverdiffraktometrie 91 A.2. Einkristall-Röntgenstrukturbestimmung 95 A.3. Rasterelektronenmikroskopie 99 A.4. Energiedispersive Röntgenspektroskopie 101 A.5. Elementaranalyse 107 A.6. Kernspinresonanzspektroskopie 108 A.6.1. Untersuchungen zur Bildung von Phosphorhalogeniden 108 A.6.2. Untersuchungen zur Bildung von Kupferphosphid 114 A.7. Raman-Spektroskopie 119 A.8. Röntgenabsorptionsspektroskopie 121 A.9. Elektronenspinresonanz-Spektroskopie 122 A.10. Elektrische Transportmessungen 123 A.11. Elektrochemische Charakterisierung 124 A.12. Wärmekapazitätsmessungen 125 A.13. Strukturbilder 126 A.14. Fotografien und Skizzen 128 A.14.1. Reaktionsapparaturen 128 A.14.2. Auflösungsversuche von elementarem Phosphor 129 B. Literaturverzeichnis 131 C. Danksagung 145 D. Liste der Publikationen 147 E. Liste der Kooperationen 149 F. Versicherung und Erklärung 151

Ionic liquids (ILs) are able to activate elements that are insoluble in common solvents. Here, the synthesis of binary antimony compounds directly from elements was explored. The 12 elements Ti-Cu, Al, Ga, In, and Te, known to form binary compounds with Sb, were reacted with Sb in [P₆₆₆₁₄]Cl under inert conditions in a closed glass flask with vigorous stirring for 16 h at 200 °C. This was immediately successful in four cases and resulted in the formation of NiSb, InSb, Cu₂Sb and Sb₂Te3. The applied reaction temperature is several hundred degrees below the temperatures required for solvent-free conversions. Compared to reactions based on diffusion in the solid state, reaction times are much shorter. The IL is not consumed and can be recycled. Since the reaction with Cu showed almost complete conversion, the influences of reaction time, temperature and medium were further investigated. Among the tested imidazolium ILs ([BMIm]Cl, [BMIm][OAc], [BDMIm]Cl) and phosphonium ILs ([P₆₆₆₁₄]X, X=Cl⁻, [DCA]⁻, [OAc]⁻, [NTf₂]⁻), those with chloride anion yielded the best results. In a diffusion experiment, Cu₂Sb formed on the copper, which indicates that antimony forms mobile species in these ILs. Supplemental crystal structure data of (As₃S₄)[AlCl₄], which was ionothermally synthesized from As and S, are reported.

Wide applications of anhydrous rare-earth (RE) trichlorides RECl₃ in organometallic chemistry, for the synthesis of optical and magnetic materials, and as catalysts require a facile approach for their synthesis. The known methods use or produce toxic substances, are complicated and have limited reliability and upscaling. It has been shown that task-specific ionic liquids (ILs) can dissolve many metal oxides without special reaction conditions at moderate temperature, making the metals accessible to downstream chemistry. Using imidazolium chloridoaluminate ILs, pure crystalline anhydrous RECl₃ (RE=La−Nd, Sm−Dy) can be synthesized in one step from RE oxides in high yield. The Lewis acidic IL acts as solvent and reaction partner. The by-product [Al₄O₂Cl₁₀]²⁻, which was detected spectroscopically, remains in solution. The reacted IL can be removed quantitatively by washing. ILs with various imidazolium cations and AlCl₃ content and the effect of temperature and reaction time were tested.

To meet the continuously rising demand for natural resources and high-value compounds, the development of new and more efficient separation technologies is important from both an economic and environmental point of view. Moreover, the detailed knowledge of adsorption phenomena can be beneficial for the development of task-specific adsorbents for gas separation processes. However, new or supplementary measurement techniques are needed to broaden the understanding of the underlying molecular mechanisms and to characterize promising materials with a fast and reliable method. Raman spectroscopy holds the potential to advance the state-of-the-art in thermophysical property research for CCS technologies in multiple ways. It can not only be utilized for fundamental research on adsorption on quasi non-porous materials due to the possibility to monitor the composition of fluid mixtures but also for the characterization of newly developed porous adsorbents. In this context, Raman spectroscopy was explored in this work to characterize the sorption capacity of translucent porous materials and to investigate the underlying mechanisms that govern sorption processes.:1 Introduction 2 Motivation 3 Experimental Background 4 Adsorption on Quasi Non-Porous Materials 5 Adsorption on Translucent Porous Materials 6 Gas Solubility in Liquids 7 Conclusion and Outlook 8 References Appendix: A Determined Peak Intensities for Adsorption Measurements B Determined Peak Intensities for Solubility Measurements C Results for Absorption Measurements D Results for Solubility Measurements E Propagation of Error / Um den ständig steigenden Bedarf an natürlichen Ressourcen und hochwertigen Verbindungen zu decken, ist die Entwicklung neuer und effizienterer Trenntechnologien sowohl aus wirtschaftlicher als auch aus ökologischer Sicht wichtig. Darüber hinaus kann die detaillierte Kenntnis von Adsorptionsphänomenen für die Entwicklung aufgabenspezifischer Adsorbentien für Gastrennverfahren von Nutzen sein. Es werden jedoch neue oder ergänzende Messverfahren benötigt, um das Verständnis der zugrunde liegenden molekularen Mechanismen zu erweitern und vielversprechende Materialien mit einer schnellen und zuverlässigen Methode zu charakterisieren. Die Raman Spektroskopie hat das Potenzial, den aktuellen Stand der Technik bei der Erforschung thermophysikalischer Eigenschaften für CCS-Technologien in mehrfacher Hinsicht zu verbessern. Sie kann nicht nur für die Grundlagenforschung zur Adsorption an quasi nicht-porösen Materialien genutzt werden, da mit ihr Zusammensetzung von Fluidgemischen bestimmt werden kann, sondern auch für die Charakterisierung neu entwickelter poröser Adsorptionsmittel. In diesem Kontext wurde die Raman-Spektroskopie in dieser Arbeit eingesetzt, um die Sorptionskapazität von transluzenten porösen Materialien zu charakterisieren und die zugrundeliegenden Mechanismen zu untersuchen, welche die Sorptionsprozesse steuern.:1 Introduction 2 Motivation 3 Experimental Background 4 Adsorption on Quasi Non-Porous Materials 5 Adsorption on Translucent Porous Materials 6 Gas Solubility in Liquids 7 Conclusion and Outlook 8 References Appendix: A Determined Peak Intensities for Adsorption Measurements B Determined Peak Intensities for Solubility Measurements C Results for Absorption Measurements D Results for Solubility Measurements E Propagation of Error

Main group polycations and transition metal clusters had traditionally been synthesized via high-temperature routes by performing reactions in melts or by CTR, at room-temperature or lower temperature by using so-called superacid solvents, and at room-temperature in benzene–GaX3 media. Considering the major problems associated with higher temperature routes (e.g. long annealing time, risk of product decomposition, and low yield) and taking into account the toxicity of benzene and liquid SO2 in room-temperature or lower temperature synthesis, a soft and sustainable chemical approach has been developed, employing a Lewis-acidic IL [bmim]Cl/AlCl3. This new alternative reaction medium has proven to be an excellent solvent system for the single–step synthesis of main group polycations and transition metal clusters. X-ray diffraction and Raman spectroscopy have been used for the structural characterization of the isolated compounds. Physical properties and quantum chemical calculations of some of the compounds have also been carried out.

We report the use of imidazolium based tunable aryl alkyl ionic liquids (TAAILs) as solvents in the Mizoroki–Heck reaction. Different commercially available palladium sources, inorganic bases, TAAILs and reaction conditions were tested for the synthesis of trans-stilbene using bromobenzene and styrene. A variety of different stilbene derivatives were synthesized with exclusive formation of the (E)-isomers and isolated yields up to 97%. We were able to optimize the reaction conditions using only 0.25 mol% of Pd(OAc)2 as the catalyst and a reaction time of 4 hours. No additional ligands or additives are used in the reaction. The catalytic system using TAAILs achieved higher yields than commercially available imidazolium and phosphonium ionic liquids, demonstrating the potential of tailored ionic liquids as a reaction medium for the Mizoroki– Heck reaction.