Electrophilic aromatic substitution by the fluorofullerene C60F18

Darwish, Adam D, Avent, Anthony G, Abdul-Sada, Ala'a K, Gol'dt, Ilya V, Hitchcock, Peter B, Kuvytchko, Igor V and Taylor, Roger (2004) Electrophilic aromatic substitution by the fluorofullerene C60F18. Chemistry - A European Journal, 10 (18). pp. 4523-4531. ISSN 0947-6539

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The FeCl3-catalysed arylation of C60F18 gives tri-substituted compounds C60F15Ar3, where Ar=phenyl, 4-tolyl, 4-methoxyphenyl, 4-phenoxyphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 2-biphylenyl and 2-fluorenyl, together with some bis- and mono-substituted product. Bis-substitution was achieved with biphenylene and fluoranthene, and mono-substitution with biphenylene (2-position), pyrene (1-position), and naphthalene (1- and 2-positions); the tris-phenyl and tris-biphenylene derivatives are fluorescent. The 2-naphthyl substituent freely rotates at 328 K, whereas rotation of the 1-naphthyl substituent is prevented by interaction of the peri-hydrogen atom with fluorine. The 1-naphthyl derivative eliminates a molecule of HF during El mass spectrometry, whilst the 2-naphthyl derivative eliminates HF and all fluorenes to give a naphthaleno[60]fullerene. The reaction rate is relatively unaffected by electron supply in the aryl rings, but no product was obtained with benzotrifluoride which defines the lower reactivity limit. The low discrimination between aromatics makes it possible to isolate derivatives having different aryl groups attached to the cage. Reactions occur mainly when the reagent solutions (or solutions in 1,2-dichlorobenzene) are evaporated to dryness. In most FeCl3-catalysed reactions, unreacted C60F18 was recovered, more if the less effective SnCl, was used as a catalyst; use of AlCl3 resulted in polyarylation and degradation of the C60F18. The structure of C60F17(1-biphenylyl) was confirmed by single-crystal X-ray analysis. Reaction of C60F18 with perylene/FeCl3/o-dichlorobenzene gave red fluorescent "tagliatelli"-like threads (up to I cm. long) of self-assembled pi-stacked tetrachloroperylene arising from chlorination by FeCl3.

Item Type: Article
Additional Information: AAS performed the detailed mass spectroscopy measurements necessary for this paper and co-author with the late RT
Schools and Departments: School of Life Sciences > Chemistry
Depositing User: Alaa Abdul-Sada
Date Deposited: 06 Feb 2012 18:49
Last Modified: 12 Jun 2012 15:25
URI: http://sro.sussex.ac.uk/id/eprint/18526
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