A Conformationally Stable π-Expanded X-Type Double Helicene Comprising Dihydropyracylene Units with Multistage Redox Behavior.

Autor: Bergner J; Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany., Borstelmann J; Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany., Cavinato LM; Technical University of Munich Campus Straubing, Chair of Biogenic Functional Materials, Schulgasse 22, 94315, Straubing, Germany., Fuenzalida-Werner JP; Technical University of Munich Campus Straubing, Chair of Biogenic Functional Materials, Schulgasse 22, 94315, Straubing, Germany., Walla C; Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.; Interdisziplinäres Zentrum für Wissenschaftliches Rechnen, Universität Heidelberg, Im Neuenheimer Feld 205, A, 69120, Heidelberg, Germany., Hinrichs H; Abteilung Chromatographie & Elektrophorese, Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim an der Ruhr, Germany., Schulze P; Abteilung Chromatographie & Elektrophorese, Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim an der Ruhr, Germany., Rominger F; Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany., Costa RD; Technical University of Munich Campus Straubing, Chair of Biogenic Functional Materials, Schulgasse 22, 94315, Straubing, Germany., Dreuw A; Interdisziplinäres Zentrum für Wissenschaftliches Rechnen, Universität Heidelberg, Im Neuenheimer Feld 205, A, 69120, Heidelberg, Germany., Kivala M; Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Feb 07; Vol. 30 (8), pp. e202303336. Date of Electronic Publication: 2023 Dec 14.
DOI: 10.1002/chem.202303336
Abstrakt: A π-expanded X-type double [5]helicene comprising dihydropyracylene moieties was synthesized from commercially available acenaphthene. X-ray crystallographic analysis revealed the unique highly twisted structure of the compound resulting in the occurrence of two enantiomers which were separated by chiral HPLC, owing to their high conformational stability. The compound shows strongly bathochromically shifted UV/vis absorption and emission bands with small Stokes shift and considerable photoluminescence quantum yield and circular polarized luminescence response. The electrochemical studies revealed five facilitated reversible redox events, including three reductions and two oxidations, thus qualifying the compound as chiral multistage redox amphoter. The experimental findings are in line with the computational studies based on density functional theory pointing towards increased spatial extension of the frontier molecular orbitals over the polycyclic framework and a considerably narrowed HOMO-LUMO gap.
(© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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