03 Fakultät Chemie

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    Asymmetric Rh diene catalysis under confinement : isoxazole ring‐contraction in mesoporous solids
    (2024) Marshall, Max; Dilruba, Zarfishan; Beurer, Ann‐Katrin; Bieck, Kira; Emmerling, Sebastian; Markus, Felix; Vogler, Charlotte; Ziegler, Felix; Fuhrer, Marina; Liu, Sherri S. Y.; Kousik, Shravan R.; Frey, Wolfgang; Traa, Yvonne; Bruckner, Johanna R.; Plietker, Bernd; Buchmeiser, Michael R.; Ludwigs, Sabine; Naumann, Stefan; Atanasova, Petia; Lotsch, Bettina V.; Zens, Anna; Laschat, Sabine
    Covalent immobilization of chiral dienes in mesoporous solids for asymmetric heterogeneous catalysis is highly attractive. In order to study confinement effects in bimolecular vs monomolecular reactions, a series of pseudo‐C2‐symmetrical tetrahydropentalenes was synthesized and immobilized via click reaction on different mesoporous solids (silica, carbon, covalent organic frameworks) and compared with homogeneous conditions. Two types of Rh‐catalyzed reactions were studied: (a) bimolecular nucleophilic 1,2‐additions of phenylboroxine to N‐tosylimine and (b) monomolecular isomerization of isoxazole to 2H‐azirne. Polar support materials performed better than non‐polar ones. Under confinement, bimolecular reactions showed decreased yields, whereas yields in monomolecular reactions were only little affected. Regarding enantioselectivity the opposite trend was observed, i. e. effective enantiocontrol for bimolecular reactions but only little control for monomolecular reactions was found.
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    A critical outlook for the pursuit of lower contact resistance in organic transistors
    (2021) Borchert, James W.; Weitz, R. Thomas; Ludwigs, Sabine; Klauk, Hagen
    To take full advantage of recent and anticipated improvements in the performance of organic semiconductors employed in organic transistors, the high contact resistance arising at the interfaces between the organic semiconductor and the source and drain contacts must be reduced significantly. To date, only a small portion of the accumulated research on organic thin‐film transistors (TFTs) has reported channel‐width‐normalized contact resistances below 100 Ωcm, well above what is regularly demonstrated in transistors based on inorganic semiconductors. A closer look at these cases and the relevant literature strongly suggests that the most significant factor leading to the lowest contact resistances in organic TFTs so far has been the control of the thin‐film morphology of the organic semiconductor. By contrast, approaches aimed at increasing the charge‐carrier density and/or reducing the intrinsic Schottky barrier height have so far played a relatively minor role in achieving the lowest contact resistances. Herein, the possible explanations for these observations are explored, including the prevalence of Fermi‐level pinning and the difficulties in forming optimized interfaces with organic semiconductors. An overview of the research on these topics is provided, and potential device‐engineering solutions are discussed based on recent advancements in the theoretical and experimental work on both organic and inorganic semiconductors.