Preparation and characterisation of C60F18

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 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 FeCl3-catalysed reactions, unreacted C60F18 was recovered, more if the less effective SnCl4 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 1 cm long) of self-assembled pi-stacked tetrachloroperylene arising from chlorination by FeCl3.

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“…Preparation of C 60 F 18 : A small-scale preparation of C 60 F 18 has been described before [22] but was prepared for this work in two ways:…”

Section: Methodsmentioning

confidence: 99%

Electrophilic Aromatic Substitution by the Fluorofullerene C₆₀F₁₈

Darwish

Avent

Abdul‐Sada

et al. 2004

Chemistry A European J

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“…Thus, a crownshaped structure of C 60 F 18 points to the C 3v symmetry [11], the consideration of T, C 3 , S 6 , and D 3d structures for C 60 F 36 has allowed for decreasing the isomer number to 63 [14], 94 isomers have been selected in the case of C 60 F 48 [13]. The justification of the assumption has been mainly based on the 19 F NMR spectra of C 60 F 18 [18], C 60 F 36 [19], and C 60 F 48 [20,21]. However, a thorough analysis of both 19 F NMR and 2d COSY spectra has shown that the structure assignment, based on the theoretical predictions, is not absolutely secure, particularly for C 60 F 36 and C 60 F 48 species (a detailed discussion see in Section 5.4).…”

Section: Introductionmentioning

confidence: 99%

Stepwise computational synthesis of fullerene C60 derivatives. Fluorinated fullerenes C60F2k

Sheka

2010

J. Exp. Theor. Phys.

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Abstract. The reactions of fullerene C 60 with atomic fluorine have been studied by unrestricted broken spin-symmetry Hartree-Fock (UBS HF) approach implemented in semiempirical codes based on AM1 technique. The calculations were focused on a sequential addition of fluorine atom to the fullerene cage following indication of the cage atom highest chemical susceptibility that is calculated at each step. The effectively-non-paired-electron concept of the fullerene atoms chemical susceptibility lays the foundation of the suggested computational synthesis. The obtained results are analyzed from energetic, symmetry, and the composition abundance viewpoints. A good fitting of the data to experimental findings proves a creative role of the suggested synthesis methodology.

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“…[26] The much longer retention time of C 60 F 18 is consistent with its greater polarity. [27] The C s symmetry of C 60 F 16 , [24] the precursor to C 60 F 18 , [26] is lower than the C 3v symmetry of C 60 F 18 , which would account for the still higher polarity of C 60 F 16 .…”

Section: Resultsmentioning

confidence: 98%

Formation, Isolation, and Spectroscopic Properties of Some Isomers of C₆₀H₃₈, C₆₀H₄₀, C₆₀H₄₂, and C₆₀H₄₄ − Analysis of the Effect of the Different Shapes of Various Helium‐Containing Hydrogenated Fullerenes on Their ³He Chemical Shifts

et al. 2003

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A complex mixture of C60H38 to C60H44 has been prepared by a much milder procedure (Benkeser reduction) than the hydrogenation procedures that have frequently been used to produce such highly hydrogenated derivatives of C60. 1H and 13C NMR spectra of fractions isolated by HPLC showed that more highly hydrogenated fullerenes exhibited signals that were shifted upfield. The opposite trend appears to hold in 3He NMR spectra of the corresponding endohedral helium compounds. The changes in the 1H, 13C, and 3He chemical shifts are reasonable for fullerenes hydrogenated to different extents. In particular, previously reported substantial changes in the shapes of the various hydrogenated fullerenes can reasonably account for the interesting trends apparent both in the 3He chemical shifts of He@C60Hx (x = 0−44) and in the HPLC retention times of the corresponding non‐helium‐containing species. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Preparation and characterisation of C60F18

Abstract: C60F18 has been prepared by reaction between [60]fullerene and potassium hexafluoroplatinate in a Knudsen cell contained within a mass spectrometer; characterisation by l9F NMR spectroscopy shows that the molecule has C3" symmetry and is isostructural with C60H18.

Cited by 139 publications

References 4 publications

Electrophilic Aromatic Substitution by the Fluorofullerene C₆₀F₁₈

Electrophilic Aromatic Substitution by the Fluorofullerene C₆₀F₁₈

Stepwise computational synthesis of fullerene C60 derivatives. Fluorinated fullerenes C60F2k

Formation, Isolation, and Spectroscopic Properties of Some Isomers of C₆₀H₃₈, C₆₀H₄₀, C₆₀H₄₂, and C₆₀H₄₄ − Analysis of the Effect of the Different Shapes of Various Helium‐Containing Hydrogenated Fullerenes on Their ³He Chemical Shifts

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Preparation and characterisation of C60F18

Abstract: C60F18 has been prepared by reaction between [60]fullerene and potassium hexafluoroplatinate in a Knudsen cell contained within a mass spectrometer; characterisation by l9F NMR spectroscopy shows that the molecule has C3" symmetry and is isostructural with C60H18.

Cited by 139 publications

References 4 publications

Electrophilic Aromatic Substitution by the Fluorofullerene C60F18

Electrophilic Aromatic Substitution by the Fluorofullerene C60F18

Stepwise computational synthesis of fullerene C60 derivatives. Fluorinated fullerenes C60F2k

Formation, Isolation, and Spectroscopic Properties of Some Isomers of C60H38, C60H40, C60H42, and C60H44 − Analysis of the Effect of the Different Shapes of Various Helium‐Containing Hydrogenated Fullerenes on Their 3He Chemical Shifts

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Electrophilic Aromatic Substitution by the Fluorofullerene C₆₀F₁₈

Electrophilic Aromatic Substitution by the Fluorofullerene C₆₀F₁₈

Formation, Isolation, and Spectroscopic Properties of Some Isomers of C₆₀H₃₈, C₆₀H₄₀, C₆₀H₄₂, and C₆₀H₄₄ − Analysis of the Effect of the Different Shapes of Various Helium‐Containing Hydrogenated Fullerenes on Their ³He Chemical Shifts