Photochemical Synthesis and Electronic Properties of Extended Corannulenes with Variable Fluorination Pattern

Dzeneta Halilovic, Maja Budanović, Zeng R. Wong, Richard D. Webster, June Huh, Mihaiela C. Stuparu

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The first family of extended and fluorinated corannulenes is prepared through a highly efficient and modular synthetic strategy. In this strategy, corannulene aldehyde could be combined with the fluorine-carrying phosphonium ylides to furnish stilbene-like vinylene precursors. A photochemically induced oxidative cyclization process of these precursors gives rise to the fluorinated and curved polycyclic aromatic hydrocarbons. A UV-vis absorption study shows that aromatic extension results in a bathochromic shift of about 12 nm. Fluorination further shifts the absorption spectrum to the red region, and a maximum shift of about 22 nm is detected for a compound carrying two trifluoromethyl groups. A cyclic and square-wave voltammetry investigation reveals that the extension of the corannulene scaffold increases the reduction potential by 0.11 V. Placement of fluorine or trifluoromethyl groups further enhances the electron affinities. In this regard, the presence of one trifluoromethyl group equals the effect of three aromatic fluorine atoms. Molecules with two trifluoromethyl groups, meanwhile, exhibit the highest reduction potentials of -1.93 and -1.83 V. These values are 0.37 and 0.46 V higher than those of the parental corannulene and demonstrate the utility of the present design concept by efficiently accessing effective electron acceptors based on the buckybowl motif.

Original languageEnglish
Pages (from-to)3529-3536
Number of pages8
JournalJournal of Organic Chemistry
Volume83
Issue number7
DOIs
Publication statusPublished - 2018 Apr 6

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Fluorination
Fluorine
Halogenation
Electronic properties
Electrons
Stilbenes
Electron affinity
Cyclization
Polycyclic Aromatic Hydrocarbons
Voltammetry
Aldehydes
Scaffolds
Absorption spectra
Atoms
Molecules
corannulene

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Photochemical Synthesis and Electronic Properties of Extended Corannulenes with Variable Fluorination Pattern. / Halilovic, Dzeneta; Budanović, Maja; Wong, Zeng R.; Webster, Richard D.; Huh, June; Stuparu, Mihaiela C.

In: Journal of Organic Chemistry, Vol. 83, No. 7, 06.04.2018, p. 3529-3536.

Research output: Contribution to journalArticle

Halilovic, Dzeneta ; Budanović, Maja ; Wong, Zeng R. ; Webster, Richard D. ; Huh, June ; Stuparu, Mihaiela C. / Photochemical Synthesis and Electronic Properties of Extended Corannulenes with Variable Fluorination Pattern. In: Journal of Organic Chemistry. 2018 ; Vol. 83, No. 7. pp. 3529-3536.
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