Synthesis of Heterocycle-Containing [60]Fullerene Derivatives

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

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.     

[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.     

[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.     

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%.     

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.     

取代基位置对羟基[60]富勒烯吡咯烷衍生物空间结构的影响

为进一步认识羟基[60]富勒烯吡咯烷衍生物的空间结构,借助密度泛函考察了羟基取代位置和取代基数量对羟基[60]富勒烯吡咯烷衍生物空间结构的影响。结果显示,5种羟基[60]富勒烯吡咯烷衍生物的LUMO均集中在[60]富勒烯上,羟基出现在邻位时其衍生物的LUMO和HOMO能量差ΔE最小,而羟基在间位时其ΔE最大。吡咯烷键长和键角并不随羟基数量的增加而呈规律性的变化,但羟基取代基位置对吡咯烷键长和键角的影响由大到小的顺序是:对位、间位、邻位。     

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.     

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.     

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).     

[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 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.     

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.     

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

Abstract

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.     

Efficient 2 + 3 Cycloaddition Approach to Synthesis of Pyridinyl Based [60]Fullerene Ligands

Abstract

[60]Fullerene reacts with azomethine ylids generated from 2‐ and 4‐picolylamines to form corresponding fulleropyrrolidines bearing pyridinyl substituents. X‐ray single crystal structure of the first dyad formed via coordination of ZnTPP to the fulleropyrrolidine nitrogen is reported.