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Preparation of a Corannulene-functionalized Hexahelicene by CopperI-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units
Published on: September 18, 2016
Helically and Linearly Fused Rylenediimide-Hexabenzocoronenes
Carolin Dusold1, Philipp Haines2, Benedikt Platzer2
1Department of Chemistry and Pharmacy, Friedrich-Alexander-University Erlangen-Nuremberg, Nikolaus-Fiebiger-Straße 10, 91058, Erlangen, Germany.
Novel donor-acceptor hybrids were synthesized by fusing perylene- and naphthalenediimides to hexabenzocoronenes (HBCs). These π-extended molecules exhibit distinct properties based on linear versus helical configurations, influencing aggregation and excited state behavior.
Area of Science:
- Organic Chemistry
- Materials Science
- Supramolecular Chemistry
Background:
- Donor-acceptor (D-A) hybrids are crucial for optoelectronic applications.
- Hexabenzocoronenes (HBCs) offer a robust platform for π-conjugation.
- Controlling molecular architecture influences material properties.
Purpose of the Study:
- To synthesize highly π-extended D-A hybrids by fusing perylene- and naphthalenediimides to HBCs.
- To investigate the impact of linear versus helical configurations on molecular properties.
- To understand the aggregation and excited state deactivation mechanisms.
Main Methods:
- Diels-Alder reactions for precursor synthesis.
- Scholl oxidation for HBC derivative formation.
- Femtosecond transient absorption spectroscopy for excited state dynamics.
- Spectroelectrochemical experiments for charge state analysis.
Main Results:
- Successful synthesis and isomer separation of HBC-based D-A hybrids.
- Formation of distinct linear and helical configurations via a benzimidazole linker.
- Significant differences in chemical, physical, and optoelectrical properties between configurations.
- Aggregation and excited state deactivation are solvent polarity-dependent.
- Charge-transfer (CT) state formation is stabilized in the helical configuration.
Conclusions:
- Molecular configuration (linear vs. helical) profoundly impacts the properties of π-extended D-A hybrids.
- The helical configuration favors CT state stabilization.
- Further investigation is needed to fully elucidate charge-separated (CS) state formation.
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