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Mechanical Stabilization of Helical Chirality in a Macrocyclic Oligothiophene

Weiland, Kevin J. and Brandl, Thomas and Atz, Kenneth and Prescimone, Alessandro and Haeussinger, Daniel and Solomek, Tomas and Mayor, Marcel. (2019) Mechanical Stabilization of Helical Chirality in a Macrocyclic Oligothiophene. Journal of the American Chemical Society, 141 (5). pp. 2104-2110.

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Official URL: https://edoc.unibas.ch/75520/

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Abstract

We introduce a design principle to stabilize helically chiral structures from an achiral tetrasubstituted [2.2]paracyclophane by integrating it into a macrocycle. The [2.2]paracyclophane introduces a three-dimensional perturbation into a nearly planar macrocyclic oligothiophene. The resulting helical structure is stabilized by two bulky substituents installed on the [2.2]paracyclophane unit. The increased enantiomerization barrier enabled the separation of both enantiomers. The synthesis of the target helical macrocycle 1 involves a sequence of halogenation and cross-coupling steps and a high-dilution strategy to close the macrocycle. Substituents tuning the energy of the enantiomerization process can be introduced in the last steps of the synthesis. The chiral target compound 1 was fully characterized by NMR spectroscopy and mass spectrometry. The absolute configurations of the isolated enantiomers were assigned by comparing the data of circular dichroism spectroscopy with TD-DFT calculations. The enantiomerization dynamics was studied by dynamic HPLC and variable-temperature 2D exchange spectroscopy and supported by quantum-chemical calculations.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Molecular Devices and Materials (Mayor)
05 Faculty of Science > Departement Chemie > Chemie > Nuclear Magnetic Resonance (Häussinger)
UniBasel Contributors:Mayor, Marcel and Brandl, Thomas and Atz, Kenneth and Prescimone, Alessandro and Solomek, Tomas and Häussinger, Daniel
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
ISSN:0002-7863
e-ISSN:1520-5126
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:21 Feb 2020 11:56
Deposited On:21 Feb 2020 11:56

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