On the thermal stability of [60]fullerene cycloadducts: retro-cycloaddition reaction of 2-pyrazolino[4,5:1,2][60]fullerenes

2-Pyrazolino[4,5:1,2][60]fullerenes undergo a thermally induced retro-cycloaddition process whose efficiency is influenced by the nature of the C-substituent. C-Aryl-N-Aryl-2-pyrazolino[60]fullerenes (2a-d) poorly undergo a thermal retro-cycloaddition reaction even in the presence of a strong dipolarophile or a metal Lewis acid which, in contrast to other fullerene derivatives, shows their remarkable thermal stability. C-Alkyl-N-Aryl-2-pyrazolino[60]fullerenes (2e-f) show a different behavior, being more vulnerable to the presence of copper triflate and leading to the retro-cycloaddition product (pristine C60) in good yield.     

Supramolecular [60]fullerene chemistry on surfaces

This critical review documents the exceptional range of research avenues in [60]fullerene-based monolayers showing unique and spectacular physicochemical properties which prompted such materials to have potential applications in several directions, ranging from sensors and photovoltaic cells to nanostructured devices for advanced electronic applications, that have been pursued during the past decade. It illustrates how progress in covalent [60]fullerene functionalisation led to the development of spectacular surface-immobilised architectures, including dyads and triads for photoinduced electron and energy transfer, self-assembled on a wide variety of surfaces. All of these molecular assemblies and supramolecular arrays feature distinct properties as a consequence of the presence of different molecular units and their spatial arrangement. Since the properties of [60]fullerene-containing films are profoundly controlled by the deposition conditions, substrate of adsorption, and influenced by impurities or disordered surface structures, the progress of such new [60]fullerene-based materials strongly relies on the development of new versatile and broad preparative methodologies. Therefore, the systematic exploration of the most common approaches to prepare and characterise [60]fullerene-containing monolayers embedded into two- or three-dimensional networks will be reviewed in great detail together with their main limitations. Recent investigations hinting at potential technological applications addressing many important fundamental issues, such as a better understanding of interfacial electron transfer, ion transport in thin films, photovoltaic devices and the dynamics associated with monolayer self-assembly, are also highlighted.     

Efficient photocleavage of DNA utilising water-soluble lipid membrane-incorporated [60]fullerenes prepared using a [60]fullerene exchange method

Various types of lipid membrane-incorporated C60 with high C60 concentrations can be prepared easily in several hours using the C60 exchange method and the photocleaving activity of cationic lipid membrane-incorporated C60 was appreciably higher than that of the C60.gamma-CDx complex.     

Fullerene-acene chemistry: single-crystal X-ray structures for a [60]fullerene-pentacene monoadduct and a cis-bis[60]fullerene adduct of 6,13-diphenylpentacene

[structure: see text]. Crystal structures of the cis-bis[60]fullerene adduct of 6,13-diphenylpentacene (with the closest carbon atoms on adjacent fullerenes only 3.065(8) angstroms apart) and the [60]fullerene-pentacene monoadduct are in remarkably close agreement with the MM2 calculated structures.     

Probing the spatial requirements for [60]fullerene-[60]fullerene π-stacking and the syn addition of [60]fullerenes across acenes

The reaction between 2 equiv of [60]fullerene and 6,8,15,17-tetraphenylheptacene-7,16-quinone leads to both cis and trans-bis[60]fullerene adducts. This result contrasts sharply with the highly diastereoselective syn additions of [60]fullerenes across 6,13-diphenylpentacene and 6,8,15,17-tetraphenylheptacene. The importance of spatially dependent [60]fullerene-[60]fullerene π-stacking interactions in promoting a syn addition of [60]fullerenes is discussed.     

[60]富勒烯[2＋3]环加成反应的研究进展

对[60]富勒烯[2＋3]环加成反应的研究进展进行了综述，并介绍了在环加成反应中使用的主要试剂及反应机理.     

Click chemistry for the efficient preparation of functionalized [60]fullerene hexakis-adducts

A Th-symmetrical C60 hexakis-adduct bearing 12 peripheral azide groups has been prepared and used to produce functionalized derivatives by the copper mediated Huisgen 1,3-dipolar cycloaddition of azides and alkynes.     

Synthesis of a linear benzo[3]phenylene-[60]fullerene dyad

The synthesis of a new linear benzo[3]phenylene-[60]fullerene dyad 1 is achieved over 10 steps in 15% overall yield by using an efficient sequence combining a double cobalt(I)-mediated cyclotrimerization with a Bingel reaction.     

Designing liquid-crystalline dendronised hexa-adducts of [60]fullerene via click chemistry

ABSTRACT

Liquid-crystalline [60]fullerodendrimers were constructed via click chemistry based on the reaction between hexa-adducts of [60]fullerene (C₆₀) bearing 12 azide groups and alkyne-terminated cyanobiphenyl dendrons of first- and second-generation. The structure of all the new compounds was confirmed by IR, UV, ¹H and ¹³C NMR spectroscopies and mass spectrometry. The mesomorphic properties were studied by polarised optical microscopy, differential scanning calorimetry and small-angle X-ray scattering. The hexa-adduct of C₆₀ functionalised with the first-generation dendrons gave rise to the formation of a smectic A phase and a rectangular columnar phase (c2mm symmetry) while the hexa-adduct of C₆₀ decorated with the second-generation dendrons displayed only a rectangular columnar phase (c2mm symmetry). Our results show that the hexa-adduct of C₆₀ is a unique synthetic platform for the design of fullerodendrimers and dendronised materials.     

Self-assembly of stimuli-responsive water-soluble [60]fullerene end-capped ampholytic block copolymer

A well-defined, water-soluble, pH and temperature stimuli-responsive [60]fullerene (C(60)) containing ampholytic block copolymer of poly((methacrylic acid)-block-(2-(dimethylamino)ethyl methacrylate))-block-C(60) (P(MAA-b-DMAEMA)-b-C(60)) was synthesized by the atom transfer radical polymerization (ATRP) technique. The self-assembly behavior of the C(60) containing polyampholyte in aqueous solution was characterized by potentiometric and conductometric titration, dynamic light scattering (DLS), and transmission electron microscopy. This amphiphilic mono-C(60) end-capped block copolymer shows enhanced solubility in aqueous medium at room and elevated temperatures and at low and high pH but phase separates at intermediate pH between 5.4 and 8.8. The self-assembly of the copolymer is different from that of P(MAA-b-DMAEMA). Examination of the association behavior using DLS revealed the coexistence of unimers and aggregates at low pH at all temperatures studied, with the association being driven by the balance of hydrophobic and electrostatic interactions. Unimers and aggregates of different microstructures are also observed at high pH and at temperatures below the lower critical solution temperature (LCST) of PDMAEMA. At high pH and at temperatures above the LCST of PDMAEMA, the formation of micelles and aggregates coexisting in solution is driven by the combination of hydrophobic, electrostatic, and charge-transfer interactions.     

Cobalt-catalyzed hydroalkylation of [60]fullerene with active alkyl bromides: selective synthesis of monoalkylated fullerenes

The Co-catalyzed hydroalkylation of C(60) with reactive alkyl bromides 1 (RBr) in the presence of Mn reductant and H(2)O at ambient temperature gave the monoalkylated C(60) (2) in good to high yields. The use of CoLn/Mn/H(2)O under Ar atmosphere is crucial for the success of the present transformation. The reaction most probably proceeds through the Co(0 or I) complex-promoted generation of a radical (R(?)) followed by addition to C(60). This hydroalkylation method was applied to the synthesis of zinc porphyrin attached C(60) (2l), dendrimer attached C(60) (2m), and fullerene dimer (2n), which were not easily available through the previously known methods.     

Reactions of [60]fullerene with 2-azidopyrimidines

The reaction of [60]fullerene with 2-azidopyrimidines affords fullerenoimidazopyrimidines, whose electron affinity is higher than that of nonmodified C₆₀.     

Methylation of [76]fullerene and [84]fullerenes; the first oxahomo derivatives of a higher fullerene

Methylation of [76]fullerene by reaction with Al-Ni alloy/NaOH followed by quenching of the intermediate anions with methyl iodide gives a mixture of methylated and methylenated products together with oxide derivatives. The major derivatives are five isomers of C(76)Me(2)(one of C(s) symmetry due to 1,6-C(76)Me(2)) and C(76)(CH(2))(n)(n= 2-4), together with corresponding mono-oxides. The single line (1)H NMR spectrum of mono-oxide C(76)Me(2)O shows it is an oxahomofullerene (ether) the first example derived from [76]fullerene, oxygen being inserted between the CMe groups in 1,6-C(76)Me(2)giving a product of C(2) symmetry. The probable structures of the unsymmetrical dimethyl derivatives have been deduced from heats of formation calculated by AM1 and density functional methods. Bis-oxide C(76)Me(4)O(2) is the first bis oxahomo[76]fullerene to be isolated and gives two equal-intensity lines in the (1)H NMR spectrum showing that it must also have C(2) symmetry; probable structures are considered. Methylation of [84]fullerene takes place less readily and only four C(84)Me(2) derivatives were isolated, two of them in quantities sufficient to show the symmetries as C(1), and either C(2) or C(s).     

Facile fullerene modification: FeCl3-mediated quantitative conversion of C60 to polyarylated fullerenes containing pentaaryl(chloro)[60]fullerenes

A facile, one-step reaction using inexpensive reagents has been developed for functionalization of [60]fullerene, where the reaction of C(60) with FeCl(3) in chlorobenzene proceeded at 25 °C with 100% conversion, yielding a mixture of polyarylated products containing pentaaryl(chloro)[60]fullerene, C(60)(C(6)H(4)Cl)(5)Cl (up to 29%) and other polyarylated fullerenes (number of aryl groups is in a range from 5 to 10).     

Mechanism of the addition reaction of alkyl azides to [60]fullerene and the subsequent N2 extrusion to form monoimino-[60]fullerenes.

The 1,3-dipolar cycloaddition of methyl azide to C60 and the subsequent nitrogen elimination from the formed triazoline intermediate to yield the aziridine adduct have been studied using semiempirical and density functional methods. The results obtained show that the addition of methyl azide to C60 takes place in the ring junction between two six-membered rings leading to a closed [6,6]-trizoline intermediate with an energy barrier of about 20 kcal mol-1 and an exothermicity of ca. 2 kcal mol-1 at the B3LYP/6-31G**//AM1 level of theory. The subsequent thermal loss of N2 takes place through a stepwise mechanism in which the cleavage of the N-N single bond precedes the breaking of the N-C bond, with a total activation energy of approximately 45 kcal mol-1. The N2 loss occurs simultaneously with the formation of the new N-C bond. During the process, the steric effects of the leaving N2 molecule prevent the addition of the nitrene substituent to the [6,6]-ring junction attacked initially and force the addition to an adjacent [5,6]-ring junction.     

Reaction of [60]fullerene with CF3COOHal affords an unusual 1,3-dioxolano-[60]fullerene

Reaction of C₆₀ with acyl hypohalogenites CF₃COOBr or CF₃COOI in the presence of water affords an orthoester-type 1,3-dioxolanofullerene in 40-50% yield. This method cannot be applied for the synthesis of 1,3-dioxolanofullerenes bearing aryl- or alkyl-groups since they undergo non-selective halogenation under the reaction conditions.     

AlCl3-catalyzed tandem acetylation of hydroarylated [60]fullerenes

The AlCl3-catalyzed acetylation of 1,2-hydrophenylated [60]fullerenes, HC60-Ar, proceeded via a sequential manner involving the acetylation at the hydrogenated fullerene carbon, the following intramolecular cyclization with the adjacent aryl group, the facile loss of water, and the second acetylation of the generated indenylidene double bond. However, the similar reaction of the hydrobiphenylated analogue brought about the normal acetylation at the terminal aromatic ring prior to the same sequential reactions as did hydrophenylated fullerenes.     

Gas-phase methylation of [60]fullerene

Direct methylation of [60]fullerene via a gas-phase reaction in a CH4/H2 atmosphere was performed using a modified hot filament chemical vapor deposition method. Pressures were varied from 10 to 60 mbar and the substrate was maintained at 690 degrees C. High-resolution matrix-assisted laser desorption ionization (MALDI) mass spectrometry analysis showed signals corresponding to C60H18-2n(H,CH3)n. Collision-induced dissociation experiments confirmed a maximum of 18 ligands possible to the [60]fullerene cage.     

Liquid-crystalline bisadducts of [60]fullerene

A second-generation cyanobiphenyl-based dendrimer was used as a liquid-crystalline promoter to synthesize mesomorphic bisadducts of [60]fullerene. Liquid-crystalline trans-2, trans-3, and equatorial bisadducts were obtained by condensation of the liquid-crystalline promoter, which carries a carboxylic acid function, with the corresponding bisaminofullerene derivatives. A monoadduct of fullerene was also prepared for comparative purposes. All the compounds gave rise to smectic A phases. An additional mesophase, which could not be identified, was observed for the trans-2 derivative. The supramolecular organization of the monoadduct derivative is governed by steric constraints. Indeed, for efficient space filling, adequacy between the cross-sectional areas of fullerene (approximately 100 A(2)) and of the mesogenic groups (approximately 22-25 A(2) per mesogenic group) is required. As a consequence, the monoadduct forms a bilayered smectic A phase. The supramolecular organization of the bisadducts is essentially governed by the nature and structure of the mesogenic groups and dendritic core. Therefore, the bisadducts form monolayered smectic A phases. The title compounds are promising supramolecular materials as they combine the self-organizing behavior of liquid crystals with the properties of fullerene.     

Fullerene-acene chemistry: diastereoselective synthesis of a cis,cis-tris[60]fullerene adduct of 6,8,15,17-tetraphenylheptacene

[structure: see text]. A one-pot, diastereoselective synthesis of a cis,cis-tris[60]fullerene adduct of 6,8,15,17-tetraphenylheptacene has been demonstrated starting from [60]fullerene and 5,7,9,14,16,18-hexahydro-6,8,15,17-tetraphenylheptacene.