Synthese funktionalisierter Cyclooctine für die kovalente und nicht-kovalente Lagensynthese auf der Silicium-Halbleiteroberfläche sowie eines Monomers für die on-surface-Synthese
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Philipps-Universität Marburg
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Abstract
As part of this work, both bisalkyne 26 and bisazide 69 were synthesized in gram-scale. In cooperation with the DÜRR group, these molecules were used to create a well-defined inorganic-organic interface on the Si(001) semiconductor surface. The modified surface 27 served as basis for the solution-based layer-by-layer synthesis that used CuAAC and SpAAC click reactions in an alternating sequence. This led to the formation of an 11-layered organic film (scheme 1).[119]
In addition, the syntheses of various cyclooctynes were investigated, which are considered candidates for the non-covalent layer-by-layer synthesis on Si(001) (figure 1). Based on a synthetic precursor of bisalkyne 26, the yet unknown cyclooctynes 134 and 135, containing a carboxylic acid and secondary amide as functional group, were synthesized successfully. The synthesis of the imide cyclooctyne 237 was realized by an elegant [2+2]-photocycloaddition.[120] First supramolecular studies based on this cyclooctyne were also carried out within the scope of this work. Additionally, the synthesis of pyrrole cyclooctyne 140 was achieved using a classic BARTON-ZARD approach for the synthesis of the heterocycle.
These cyclooctynes can now be investigated for their potential use in the non-covalent layer-by-layer synthesis on Si(001).
The syntheses of barbituric acid cyclooctyne 136, uracil cyclooctyne 137 and lactam cyclooctyne 138 were also investigated as part of this work, but did not lead to the planned target structured due to various reasons. The synthesis of barbituric acid cyclooctyne 136 failed primarily due to its extremely poor solubility as soon as the heterocycle in 162 was formed. In the case of lactam cyclooctyne 138, the cyclic alkyne could not be successfully isolated, because the lactam moiety led to transannular side reactions during the reaction. The precursors 176 and 201 of uracil cyclooctyne could be prepared, but uracil-typical side reactions occurred during bromination of 176 and ring-closing metathesis of 201 did not form cyclic vinyl bromide (scheme 2).
Also, the diiodo-terphenyl 141 (Fig. 2) was synthesized successfully. This monomer serves as a potential precursor for the synthesis of the biphenylene network on the Al2O3-surface, which is investigated within the collaboration with the GOTTFRIED group.
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Created: 2025Issued: 2025-06-23Updated: 2025-06-23
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Fachbereich Chemie
Publisher
Philipps-Universität Marburg
Language
ger
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DoctoralThesis
Keywords
supramolecular chemistrycyclooctyneslayer-by-layer synthesisorganic synthesissemiconductorsSi(001)
DFG-subjects
Si(001)organische SyntheseCyclooctineHalbleiterLagensyntheseLayer-by-Layer SyntheseSupramolekulare Chemie
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540
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Scharf, Dominik (0009-0009-5062-9556): Synthese funktionalisierter Cyclooctine für die kovalente und nicht-kovalente Lagensynthese auf der Silicium-Halbleiteroberfläche sowie eines Monomers für die on-surface-Synthese. : Philipps-Universität Marburg 2025-06-23. DOI: https://doi.org/10.17192/z2025.0234.
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This item has been published with the following license: In Copyright