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Part 1: Document Description
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Citation |
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Title: |
Chirale polyzyklische aromatische Kohlenwasserstoffe mit Affensattel-Topologie [Data] |
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Identification Number: |
doi:10.11588/data/SHVINO |
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Distributor: |
heiDATA |
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Date of Distribution: |
2022-12-05 |
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Version: |
1 |
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Bibliographic Citation: |
Kirschbaum, Tobias, 2022, "Chirale polyzyklische aromatische Kohlenwasserstoffe mit Affensattel-Topologie [Data]", https://doi.org/10.11588/data/SHVINO, heiDATA, V1 |
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Citation |
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Title: |
Chirale polyzyklische aromatische Kohlenwasserstoffe mit Affensattel-Topologie [Data] |
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Identification Number: |
doi:10.11588/data/SHVINO |
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Authoring Entity: |
Kirschbaum, Tobias (Institute of Organic Chemistry, Heidelberg University) |
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Grant Number: |
SFB 1249 (TP-A04) |
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Distributor: |
heiDATA |
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Access Authority: |
Kirschbaum, Tobias |
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Access Authority: |
Mastalerz, Michael |
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Access Authority: |
Elbert, Sven |
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Holdings Information: |
https://doi.org/10.11588/data/SHVINO |
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Study Scope |
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Keywords: |
Chemistry, polycyclic aromatic hydrocarbons, N-heteroarene, chirality, monkey saddle, negative curvature |
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Abstract: |
In this thesis, the first chiral polycyclic aromatic hydrocarbon (PAH) with a monkey saddle topology is presented. Starting from a truxene building block that is readily preparatively accessible, the monkey saddle PAH could easily be obtained in three steps. By using additional functionalized precursors, a series of twelve derivatives has been obtained and characterized. Solid-state structures confirmed the three-dimensional shape of the PAHs unambiguously, which is induced by the five-, six- and eight-membered rings. This makes the PAH a section of a Mackay-type crystal. Due to the curvature, the target compounds exhibit triple axial chirality. Separation of the enantiomers was possible and characterization of these via CD spectroscopy and the investigation of racemization revealed half-lives ranging from a few milliseconds to several days. In addition, first attempts to synthesize Mackay-like cage compounds have been conducted and provided important insights for future projects. A deeper insight into the properties of the curved PAHs was achieved by the isosteric exchange of three CH groups with nitrogen. Its effect could be studied in detail and led to a stabilization of the enantiomers towards a half-life of two months. Furthermore, a rearrangement was developed that lead to a chiral molecular basket whose enantiomers do not longer racemize at room temperature. The experimental results were supported and extended by a large number of quantumchemical calculations. A second truxene precursor formed the basis on which the preparation of a system with three azulene units succeeded. Synthetic difficulties on the way to the target compound could be circumvented and thus a keto-functionalized PAH has been obtained, which forms two separable diastereomers. The azulene PAH represents a model of a graphene defect due to the five- and seven-membered rings and was studied in terms of its photophysical and electrochemical properties as well as compared with isomeric compounds. Confirmation of the structures of all three target compounds by X-ray structural analysis was also successful. First experiments on post-functionalization were performed so that future projects can build on them. |
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Other Study Description Materials |
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Related Publications |
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Citation |
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Title: |
T. Kirschbaum, Chirale polyzyklische aromatische Kohlenwasserstoffe mit Affensattel-Topologie, Dissertation, Ruprecht-Karls-Universität Heidelberg, 2022. |
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Identification Number: |
10.11588/heidok.00032383 |
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Bibliographic Citation: |
T. Kirschbaum, Chirale polyzyklische aromatische Kohlenwasserstoffe mit Affensattel-Topologie, Dissertation, Ruprecht-Karls-Universität Heidelberg, 2022. |
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Additional DFT calculations.zip |
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