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- ItemDynamics, cation conformation and rotamers in guanidinium ionic liquids with ether groups(Amsterdam : Elsevier, 2023) Rauber, Daniel; Philippi, Frederik; Morgenstern, Bernd; Zapp, Josef; Kuttich, Björn; Kraus, Tobias; Welton, Tom; Hempelmann, Rolf; Kay, Christopher W.M.Ionic liquids are modern materials with a broad range of applications, including electrochemical devices, the exploitation of sustainable resources and chemical processing. Expanding the chemical space to include novel ion classes allows for the elucidation of novel structure-property relationships and fine tuning for specific applications. We prepared a set of ionic liquids based on the sparsely investigated pentamethyl guanidinium cation with a 2-ethoxy-ethyl side chain in combination with a series of frequently used anions. The resulting properties are compared to a cation with a pentyl side chain lacking ether functionalization. We measured the thermal transitions and transport properties to estimate the performance and trends of this cation class. The samples with imide-type anions form liquids at ambient temperature, and show good transport properties, comparable to imidazolium or ammonium ionic liquids. Despite the dynamics being significantly accelerated, ether functionalization of the cation favors the formation of crystalline solids. Single crystal structure analysis, ab initio calculations and variable temperature nuclear magnetic resonance measurements (VT-NMR) revealed that cation conformations for the ether- and alkyl-chain-substituted are different in both the solid and liquid states. While ether containing cations adopt compact, curled structures, those with pentyl side chains are linear. The Eyring plot revealed that the curled conformation is accompanied by a higher activation energy for rotation around the carbon-nitrogen bonds, due to the coordination of the ether chain as observed by VT-NMR.
- ItemUltrathin gold nanowires for transparent electronics: breaking barriers(Amsterdam : Elsevier, 2016) Gonzalez-Garcia, Lola; Maurer, Johannes H.M.; Reiser, Beate; Kanelidis, Ioannis; Kraus, TobiasNovel types of Transparent Conductive Materials (TCMs) based on metal nanostructures are discussed. Dispersed metal nanoparticles can be deposited from liquids with moderate thermal budgets to form conductive films that are suitable for thin-film solar cells, displays, touch screens, and nanoelectronics. We aim at new TCMs that combine high electrical conductivity with optical transparency and mechanical flexibility. Wet-processed films of randomly arranged metallic nanowires networks are commercially established and provide a relatively cost-effective, scalable production. Ultrathin gold nanowires (AuNWs) with diameters below 2 nm and high aspect ratios have recently become available. They combine mechanical flexibility, high optical transparency, and chemical inertness. AuNWs carry oleylamine capping ligands from synthesis that cause high contact resistances at their junctions. We investigated different annealing processes based on temperature and plasma treatment, to remove the ligands after deposition and to allow electrical conductivity. Their effect on the resulting nanostructure and on the material properties was studied. Scanning Electron Microscopy (SEM) and optical spectroscopy revealed changes in the microstructure for the different post-treatments. We found that the conductivity and the stability of the TCM depended strongly on its final microstructure. We demonstrate that the best results are obtained using H2-plasma treatment.