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J Org Chem. 2018 Apr 6;83(7):3529-3536. doi: 10.1021/acs.joc.7b03146. Epub 2018 Mar 8.

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

Author information

1
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences , Nanyang Technological University , 21-Nanyang Link , 637371 , Singapore.
2
Department of Chemical and Biological Engineering , Korea University , Seoul 02841 , Korea.
3
School of Materials Science and Engineering , Nanyang Technological University , 50 Nanyang Avenue , 639798 , Singapore.

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.

PMID:
29518317
DOI:
10.1021/acs.joc.7b03146

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