Regiochemistry of Azide Additions to [70]Fullerene

Abstract

In this paper we report for the first time on the reaction of C₇₀ with alkyl azides and show that the [3+2]-cycloaddition occurs preferably at bond 7 followed by bond 5 to give two regioisomeric A/B-triazolines and one C/C-triazoline Thermal extrusion of N₂ from these triazolines leads to open [5,6]-bridged iminofullerenes as A/A- and B/C-isomers as well as to the ring closed [6,6]-bridged analogues as A/B- and C/C-isomers. These results are in line with the corresponding thermal reaction of C₇₀ with diazomethane.     

Supramolecular Complexes between Fullerene [60]- and [70], and resorcinarene

Abstract

New complexes 2 and 3 between [60]- and [70] fullerenes with resorcinarene 1 were prepared and characterized by spectroscopic methods. Resorcinarene 1 was studied in solution by NMR and in the solid state by CP-MAS NMR and X-ray diffraction. The macrocycle 1 can guest one [60]- or [70] fullerene molecule in its structure. For the complexes 2 and 3, π-π, CH-π and n-π interactions were observed by ¹³C CP-MAS and FTIR analysis data.     

Supramolecular Complexes between Fullerene [60]- and [70], and resorcinarene

New complexes 2 and 3 between [60]- and [70] fullerenes with resorcinarene 1 were prepared and characterized by spectroscopic methods. Resorcinarene 1 was studied in solution by NMR and in the solid state by CP-MAS NMR and X-ray diffraction. The macrocycle 1 can guest one [60]- or [70] fullerene molecule in its structure. For the complexes 2 and 3, π-π, CH-π and n-π interactions were observed by ¹³C CP-MAS and FTIR analysis data.     

Trifluoromethylation of [60]- and [70]Fullerene in the Ionization Chamber of a Mass Spectrometer

Both [60]- and [70]fullerene react with either the Scherer radical (perfluorodiisopropylethylmethyl, C₉F₁₉), a mixture of branched perfluorononenes (C₉F₁₈, the product of hexafluoropropene trimerization), or β-fluorosulphatotetrafluoroethyldiheptafluoroisopropylmethyl radical (C₉F₁₈OSO₂F) in the ionization chamber of a mass spectrometer to give the positive parent ions of trifluoromethylation products, the reaction being accompanied by hydrogen addition. The reaction occurs at least partly on the walls of the ionization chamber, by a radical mechanism employing CF₃ radicals formed from the radical reactants both thermally and under electron impact; only the latter route occurs with the perfluorononenes.     

Trifluoromethylation of [60]- and [70]Fullerene in the Ionization Chamber of a Mass Spectrometer

Abstract

Both [60]- and [70]fullerene react with either the Scherer radical (perfluorodiisopropylethylmethyl, C₉F₁₉), a mixture of branched perfluorononenes (C₉F₁₈, the product of hexafluoropropene trimerization), or β-fluorosulphatotetrafluoroethyldiheptafluoroisopropylmethyl radical (C₉F₁₈OSO₂F) in the ionization chamber of a mass spectrometer to give the positive parent ions of trifluoromethylation products, the reaction being accompanied by hydrogen addition. The reaction occurs at least partly on the walls of the ionization chamber, by a radical mechanism employing CF₃ radicals formed from the radical reactants both thermally and under electron impact; only the latter route occurs with the perfluorononenes.     

Kinetic Behavior of Addition Reactions to [60]Fullerene

The addition reactions of [60]fullerene to benzyl amine and anthracene were studied by using spectrophotometry. The kinetic measurements show minima if the absorbance at a wavelength of 595 nm is plotted versus time. The minima obtained from the spectrophotometric kinetic measurements can be attributed to the formation of intermediates of C₆₀ due to the single-electron transfer mechanism for the amine addition and electron deloalization processes for the concerted [2 + 4]cyclo-addition.     

Synthesis of Heterocycle-Containing [60]Fullerene Derivatives

Abstract

Fullerene functionalization with heterocycles is reviewed, focusing attention on cycloaddition methodology and oxidative heterocyclization. ^{1 1}This paper was presented before the Symposium 3 on ‘Expanded Horizons of Fullerene Science and Technology’ organized by L. Y. Chiang, E.Osawa, H. Terrones and M. Saunders at the 4th International Conference on Advanced Materials (ICAM-IV), Aug. 27 to Sept. 1, 1995, Cancun, Mexico.

     

Synthesis of Heterocycle-Containing [60]Fullerene Derivatives

Fullerene functionalization with heterocycles is reviewed, focusing attention on cycloaddition methodology and oxidative heterocyclization.¹     

[60]富勒烯环加成反应研究进展

综述了[60]富勒烯[2 1]环加成反应、[2 2]环加成反应、[2 3]环加成反应以及[4 2]环加成反应的典型反应、反应试剂以及反应机理,并展望了富勒烯的研究前景和发展方向.     

Nanoencapsulation of [60]Fullerene with the Cavitand Cucurbit[7]uril

Novel supramolecular nanocapsules consisting of [60]fullerene and the macrocycle cucurbit[7]uril via self-assembly are reported. The nanocapsules, which were synthesized in a two-phase reaction at room temperature, were obtained in good yields. The stoichiometry of the product was found to be 1:2.     

All-Carbon [60]Fullerene Oligomers of Pearl-Necklace Type

The formation of all-carbon [60]fullerene derivatives was observed in the course of the thermolysis of methano-fullerene derivatives. IR, UV-Vis, GPC, ¹³C-NMR, TG-MS, TOF-MS and STM data are consistent with the formation of all-carbon [60]fullerene oligomers without a direct connection between fullerene cages but through one or two carbon atoms as bridges. Molecular masses up to 8000 amu have been detected by mass spectroscopy.     

All-Carbon [60]Fullerene Oligomers of Pearl-Necklace Type

Abstract

The formation of all-carbon [60]fullerene derivatives was observed in the course of the thermolysis of methano-fullerene derivatives. IR, UV-Vis, GPC, ¹³C-NMR, TG-MS, TOF-MS and STM data are consistent with the formation of all-carbon [60]fullerene oligomers without a direct connection between fullerene cages but through one or two carbon atoms as bridges. Molecular masses up to 8000 amu have been detected by mass spectroscopy.     

[60]Fullerene as a Novel Photoinduced Antibiotic

Abstract

The antibacterial activity of [60]fullerene (C₆₀), dissolved with poly(vinylpyrrolidone) K30 (PVP), was studied. Under photo‐irradiation, C₆₀/PVP aqueous solutions showed antibacterial activity, whereas PVP solution alone or fullerene solutions in the absence of light showed no activity. These results reveal that C₆₀ is a potentially good device as a photoinduced antibacterial agent.     

[60]Fullerene Amino Acids and Related Derivatives

This paper is a review of the literature concerning the preparation of [60]fullerene amino acid and peptide derivatives. The structure and applications of these derivatives to the biological and Material sciences is also presented.     

[60]Fullerene as a Novel Photoinduced Antibiotic

The antibacterial activity of [60]fullerene (C₆₀), dissolved with poly(vinylpyrrolidone) K30 (PVP), was studied. Under photo-irradiation, C₆₀/PVP aqueous solutions showed antibacterial activity, whereas PVP solution alone or fullerene solutions in the absence of light showed no activity. These results reveal that C₆₀ is a potentially good device as a photoinduced antibacterial agent.     

[60]Fullerene Amino Acids and Related Derivatives

Abstract

This paper is a review of the literature concerning the preparation of [60]fullerene amino acid and peptide derivatives. The structure and applications of these derivatives to the biological and Material sciences is also presented.     

Synthesis of High-Molecular-Weight [60]Fullerene Pearl-Necklace Polyamides Derived from Equatorial [60]fullerenobisacetic Acid

Abstract

A series of [60]fullerene pearl-necklace polyamides, consisting of equatorial-[60]fullerenobisacetic acid and various chromophoric aromatic diamines, were synthesized by a phosphorylation route using large amounts of triphenyl phosphite and pyridine as condensing reagents with stepwise addition of the condensing reagents. In the present polymers, [60]fullerene pearls and diamine linkers were attached to one another by cyclopropane connectors. The polyamides had weight-average molecular weights (M_w)of 4.5-5.0×10⁴ g/mol and inherent viscosities (n _inh) of 0.3-0.4 dL/g in N, N-dimethylacetamide (DMAc) at 30 °C. They had glass transition temperatures at 30-125 °C and decomposition temperatures at 300-310 °C. The UV-VIS spectra in DMAc exhibited broad absorption with λ_max at 310-390 nm tailing to longer wavelengths.     

Synthesis of High-Molecular-Weight [60]Fullerene Pearl-Necklace Polyamides Derived from Equatorial [60]fullerenobisacetic Acid

A series of [60]fullerene pearl-necklace polyamides, consisting of equatorial-[60]fullerenobisacetic acid and various chromophoric aromatic diamines, were synthesized by a phosphorylation route using large amounts of triphenyl phosphite and pyridine as condensing reagents with stepwise addition of the condensing reagents. In the present polymers, [60]fullerene pearls and diamine linkers were attached to one another by cyclopropane connectors. The polyamides had weight-average molecular weights (M_w)of 4.5-5.0×10⁴ g/mol and inherent viscosities (n_inh) of 0.3-0.4 dL/g in N, N-dimethylacetamide (DMAc) at 30 °C. They had glass transition temperatures at 30-125 °C and decomposition temperatures at 300-310 °C. The UV-VIS spectra in DMAc exhibited broad absorption with λ_max at 310-390 nm tailing to longer wavelengths.     

Photochemical Reaction of Furans in the Presence of [60] Fullerene

The first evidence was presented which supports a photochemical pathway during the reaction of furan derivatives in the presence of C₆₀, which was formerly believed to proceed via a thermal [2+4]-concerted cycloaddition reaction of furans with C₆₀. LD-TOF-MS, UV-vis, FT-IR and ¹H-, ¹³C-NMR spectra showed that     

Reaction of [60]Fullerene with Terbium(IV) Fluoride

Abstract

A reaction between [60]fullerene and terbium(IV) fluoride is shown to be a new example of the thermally induced disruption of the fullerene skeleton. “Hyperfluorination” occurs at the elevated temperature (350° C) thereby producing species C₆₀ Fx (x > 60). The fluorination products were characterized by mass spectrometry and IR spectroscopy methods.