Synthesis and Chemical Transformations of the Diels-Alder Adduct of [60] Fullerene and 4-Amino-O-quinodimethane

Diels-Alder reaction of 4-amino-o-quinodimethane (6) with [60]fullerene (1) affords the thermally stable and chemically reactive adduct 7(n). The nucleophilic amino group of 7(n) is well suited for the covalent attachment of different molecules to the [60]fullerene core by further chemical reactions.     

Scalable, Solution Phase Synthesis of the Trans-1 Bisanthracene Adduct of [60]Fullerene

A new, scalable, one-pot solution phase synthesis of the D_2 h symmetric trans-1 bisanthracene adduct of [60]fullerene is described. The highly regioselective reaction utilizes commercially available 9,10-dihydroanthracene, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and [60]fullerene and exhibits an unusual temperature dependence.     

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     

Diels-Alder Reactions of the [60]Fullerene: From Regularly Functionalized Carbon Spheres to Cyclophanes

Abstract

Diels-Alder reactions allow the regioselective preparation of various derivatives of the [60]fullerene (1) with exohedral functionalization. A symmetric sixfold [2+4]-cycloaddition of 1,3-dienes to 1 opens direct synthetic access to hydrocarbons with a novel cyclophane structure.     

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.     

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.     

Diels-Alder Reactions of the [60]Fullerene: From Regularly Functionalized Carbon Spheres to Cyclophanes

Diels-Alder reactions allow the regioselective preparation of various derivatives of the [60]fullerene (1) with exohedral functionalization. A symmetric sixfold [2+4]-cycloaddition of 1,3-dienes to 1 opens direct synthetic access to hydrocarbons with a novel cyclophane structure.     

Electrochemical Synthesis and Transformations of Substituted Methano[60]fullerenes

Abstract

61‐(Dimethoxyphosphoryl)‐61‐(methoxycarbonyl)methano[60]fullerene was produced by using the joint electrochemical reduction of fullerene C₆₀ and (dimethoxyphosphoryl)methoxycarbonyldibromomethane. A few steps of reduction were detected for phosphorylated methano[60]fullerenes. When two electrons per molecule are transferred, the methano fragment is rapidly eliminated (retro‐Bingel reaction). This process involves the step‐by‐step cleavage of two C–C bonds of exo‐carbon with the fullerene shell in combination with the stepwise transfer of other two electrons and a proton to form finally the carbanion of the methano fragment and fullerene dianion.     

Diels-Alder Reaction of [60]Fullerene with Dienes Having an Ester Substituent at 1-Position

Abstract

Treatment of [60]fullerene with ethyl trans, trans-hexa-2,4-dienoate (1) and methyl trans, trans-octa-2,4-dienoate (2) at 70 ～ 100 °C afforded products 3 and 4, respectively, which are resulted from Diels-Alder addition of the dienoates to a 6/6 ring junction of [60]fullerene.     

Diels-Alder Reaction of [60]Fullerene with Dienes Having an Ester Substituent at 1-Position

Treatment of [60]fullerene with ethyl trans, trans-hexa-2,4-dienoate (1) and methyl trans, trans-octa-2,4-dienoate (2) at 70 ∼ 100 °C afforded products 3 and 4, respectively, which are resulted from Diels-Alder addition of the dienoates to a 6/6 ring junction of [60]fullerene.     

Functionalization of [60]Fullerene Using a Novel Chemical Vapor Modification Method

Abstract

Gas phase reactions of [60]fullerene with hydrogen atoms and/or methyl radicals have been performed by hot filament chemical vapor modification (CVM) to produce hydrogenated and/or methylated [60]fullerene. The CVM process parameters such as the time of reaction, pressure, and percentage of methane diluted in hydrogen have been varied so as to obtain the addended fullerene reaction products. Mass spectrometry and ¹H NMR techniques were used to characterize the reaction products obtained.     

Synthesis and Characterisation of Some New Ferrocenyl- and Ferrocenylalkynyl-[60]Fullerene Compounds

We report the synthesis and characterisation of a series of ferrocenylfullerene compounds, and some new ferrocene derivatives required as intermediates. The new fullerene species are Fc-[60]fullerene, (8); Fc-C=C-[60]fullerene, (10); Fc-C=C-C=C-[60]fullerene, (12); and (η-C₅H₄SiBu₃)Fe(η-C₅H₄)-[60]fullerene, (14).     

Synthesis of Calix[4, 5, 6] Resorcinarenes Using Fullerene C60 as Template

We present a new use of fullerene C₆₀ as a template for the synthesis of cyclic resorcinarenes, The cyclocondensation of 2-methyl-resorcinol with benzaldehyde and hexanal in THF, catalyzed by AlCl₃, in the presence of 1%, 5%, and 10% fullerene C₆₀, produces calix[4], [5], and [6] resorcinarenes, with the pentamer and hexamer as the major products. The resorcinarenes were characterized by ¹H, ¹³C NMR, FTIR, FAB⁺ mass spectrometry, and elemental analysis.     

Synthesis of Calix[4, 5, 6] Resorcinarenes Using Fullerene C60 as Template

Abstract

We present a new use of fullerene C₆₀ as a template for the synthesis of cyclic resorcinarenes, The cyclocondensation of 2‐methyl‐resorcinol with benzaldehyde and hexanal in THF, catalyzed by AlCl₃, in the presence of 1%, 5%, and 10% fullerene C₆₀, produces calix[4], [5], and [6] resorcinarenes, with the pentamer and hexamer as the major products. The resorcinarenes were characterized by ¹H, ¹³C NMR, FTIR, FAB⁺ mass spectrometry, and elemental analysis.     

Synthesis, Photophysical and Photovoltaic Properties of New [60]Fullerene Pyrrolidine Derivatives

Two new [60]fullerene pyrrolidine derivatives 2 and 3 were synthesized and characterized by ¹H NMR, ¹³C NMR and MS. Their photophysical processes have been investigated by using laser flash photolysis. The experiments show quenching of oligomer singlet excited state and the evidence of the fullerene singlet excited emission. And the intramolecular of electron transfer and also energy transfer of 2 and 3 occurred and the triplet excited state of fullerene moiety in 2 and 3 have different lifetime due to their different structures. A photovoltaic device using compound 2 as the only photoactive material has also been investigated which showed the energy conversion efficiency is 0.011%.     

[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 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 Heterocycle-Containing [60]Fullerene Derivatives. II.1 Recent Progress in [4 2]- and [3 2]-Cycloaddition Routes

Recent progress of synthesis of C₆₀ derivatives functionalized with hetero-cycles is reviewed, focusing attention on [4+2]- and [3+2] cycloaddition methodologies and oxidative heterocyclization.     

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.