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Electrophilic Aromatic Substitution by the Fluorofullerene C 60 F 18
Author(s) -
Darwish Adam D.,
Avent Anthony G.,
AbdulSada Ala'a K.,
Gol'dt Ilya V.,
Hitchcock Peter B.,
Kuvytchko Igor V.,
Taylor Roger
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200400036
Subject(s) - chemistry , substituent , aryl , biphenylene , reactivity (psychology) , medicinal chemistry , electrophilic aromatic substitution , electrophilic substitution , substitution reaction , naphthalene , photochemistry , derivative (finance) , organic chemistry , alkyl , phenylene , medicine , alternative medicine , pathology , financial economics , economics , polymer
The FeCl 3 ‐catalysed arylation of C 60 F 18 gives tri‐substituted compounds C 60 F 15 Ar 3 , 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 EI 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 FeCl 3 ‐catalysed reactions, unreacted C 60 F 18 was recovered, more if the less effective SnCl 4 was used as a catalyst; use of AlCl 3 resulted in polyarylation and degradation of the C 60 F 18 . The structure of C 60 F 17 (1‐biphenylyl) was confirmed by single‐crystal X‐ray analysis. Reaction of C 60 F 18 with perylene/FeCl 3 / o ‐dichlorobenzene gave red fluorescent “tagliatelli”‐like threads (up to 1 cm long) of self‐assembled π‐stacked tetrachloroperylene arising from chlorination by FeCl 3 .