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Updated: Jun 25, 2026

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Published on: February 7, 2017
Shape-persistent macrocycles comprising perfluorinated benzene subunits: synthesis, aggregation behaviour and
Lijin Shu1, Marcel Müri, Ralph Krupke
1Forschungzentrum Karlsruhe GmbH, Institute for Nanotechnology, P. O. Box 3640, D-76021 Karlsruhe, Germany.
Researchers synthesized shape-persistent macrocycles (SPMs) with fluorinated units. Aggregation behavior was studied, revealing that the spatial arrangement of fluorinated subunits is crucial for aggregate formation and properties.
Area of Science:
- Supramolecular Chemistry
- Organic Synthesis
- Materials Science
Background:
- Shape-persistent macrocycles (SPMs) are crucial in supramolecular chemistry.
- Functionalization of SPMs enhances solubility and allows for tailored properties.
- Tetrafluorobenzene and benzene subunits offer unique electronic characteristics.
Purpose of the Study:
- To synthesize novel SPMs with varying tetrafluorobenzene and benzene content.
- To investigate the aggregation behavior of these SPMs in solution.
- To understand the influence of structural arrangement on aggregation thermodynamics.
Main Methods:
- Modular synthesis utilizing palladium/copper-catalyzed acetylene coupling reactions.
- Functionalization with peripheral hexyl chains for improved solubility.
- Characterization of aggregation using concentration/temperature-dependent 1H-NMR and vapor pressure osmometry.
Main Results:
- SPMs containing electron-deficient tetrafluorobenzene units (SPMs 2-6) exhibited aggregation in chloroform.
- Dimerization was prevalent for SPMs 3-6, while SPM 2 formed larger aggregates.
- Aggregation was enthalpically driven, with spatial arrangement of fluorinated units significantly impacting thermodynamic parameters.
- SPM 3 formed micro-scaled hexagonal rods upon heating in toluene.
Conclusions:
- The presence and spatial arrangement of tetrafluorobenzene units are key determinants of SPM aggregation.
- Thermodynamic driving forces for aggregation are primarily enthalpic.
- Structural nuances within SPMs significantly influence their self-assembly behavior and potential for materials applications.
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