A DFT study on Diels–Alder cycloadditions of trans‐1,3‐butadiene to C60 and C70

Investigation of the relative reactivity of bonds in fullerenes will provide fundamental theory for the design of fullerene‐based materials. We have theoretically investigated the reactivity of the Diels–Alder (DA) cycloaddition of cis‐1,3‐butadiene to all types of bonds in C₆₀ and C₇₀ using the M06‐2X hybrid density functional theory (DFT) calculations (J. Phys. Org. Chem. 2012, 25 850–855) and have pointed out that the DA cycloadditions of cis and trans forms of 1,3‐butadiene to ethylene have a specially intimate relationship (J. Phys. Org. Chem. 2014, 27 652–660). For the aim of telling a whole story of the DA cycloaddition concerning C₆₀ and C₇₀, the DA cycloadditions of trans‐1,3‐butadiene to all types of bonds in C₆₀ and C₇₀ were explored at the same theoretical level as those of the cis‐1,3‐butadiene. The calculated results related with the trans‐ and cis‐1,3‐butadienes were compared. The potential energy curves of DA cycloadditions of trans‐ and cis‐1,3‐butadiene to C₆₀ and C₇₀ were discussed. The distortion–interaction energy model was employed to elucidate the origin of different reactivity of all kinds of C?C bonds. The solvent effects were examined using the continuum solvent model. These current results, along with our previous research, will help to obtain an overall view of the DA cycloadditions of 1,3‐butadiene to C₆₀ and C₇₀. Copyright © 2014 John Wiley & Sons, Ltd.     

A theoretical study on the interaction between well curved conjugated systems and fullerenes smaller than C60 or larger than C70

A large body of data exists about the interaction between curved π systems and C₆₀ or C₇₀. However, little is known about the interaction with fullerenes smaller than C₆₀ or larger than C₇₀. To fill that gap, we studied, by means of density functional theory (M06‐2X), the interaction between corannulene, pentaindenocorannulene, C₆₀H₂₈ buckycatcher and the following fullerenes: C₄₄, C₅₀, C₈₀, C₉₀, C₁₀₀, C₁₈₀ and C₂₄₀. For fullerenes smaller than C₆₀, their high reactivity facilitated the covalent addition to the hosts assayed. Yet, the reaction energies determined for the covalent addition were comparable to those calculated for the formation of supramolecular complexes. Thus, the receptor may host a fullerene and at least have another one attached. As expected, for fullerenes larger than C₇₀, supramolecular complexes were preferred over covalent assemblies. The binding energies with bowls increased with the size of the fullerenes in a non‐monotonic fashion since they depended on the shape of the fullerene. Indeed, for one C₈₀ isomer, it is possible to find a region which forms a complex with corannulene that is stronger than C₆₀@corannulene, while another region exists whose interaction with corannulene is weaker. As the size of the fullerene becomes larger, ball–socket interactions are weakened, and CH–π interactions become important, accounting for the large interaction determined for corannulene and graphene. Finally, for the buckycatcher, the maximum encapsulation energy among the fullerenes assayed was displayed by C₉₀. The fullerenes C₈₀, C₉₀ and C₁₀₀ formed complexes with the buckycatcher which are stronger than in C₆₀@buckycatcher. Copyright © 2014 John Wiley & Sons, Ltd.     

Rheological Behavior of Poly(vinylpyrrolidone)/Fullerene C60 Complexes in Aqueous Medium

Aqueous solutions of complexes formed between poly(vinylpyrrolidone) (PVP), as a matrix polymer, and fullerene C₆₀ were investigated. The effect of the external hydrodynamic field on the supermolecular assemblies formed by the complexes was analyzed. Despite the low content in the complexes (1.5 mass%), fullerene significantly modified the viscosity of aqueous PVP. Thus, the dynamic viscosity of the PVP/C₆₀ complexes grew faster than that of the pure PVP upon increasing the PVP/C₆₀ concentration. The difference in viscosities is especially pronounced for semidilute solutions. As a possible explanation, it is assumed that fullerenes act as crosslinks, in addition to the physical entanglements of the PVP macromolecules, which appear in the vicinity of the crossover concentration. Shear flow corresponding to the high shear rates destroyed fullerene‐induced intermolecular crosslinks in PVP/C₆₀ solutions.     

On the Supermolecular Structure of Fullerene C60 Solutions

Small angle X‐ray scattering (SAXS) and wide angle X‐ray scattering (WAXS) techniques were used for investigation of fullerene C₆₀ solutions in toluene and p‐xylene. On all SAXS curves, intensity decreases to some constant value of I_C with increase of scattering angle. The value of I_C depends on concentration non‐monotonically: it first slightly increases, then drops sharply to some minimal value, and then increases again. A qualitative explanation of such dependence is offered. It is supposed that the presence of fullerene C₆₀ in solution suppresses thermal fluctuations of density in the solvent. In combination with the X‐ray data the results obtained for solutions of fullerene C₆₀ by various others techniques (calorimetry, densimetry, etc.) are discussed. Possible models of a supermolecular structure of fullerene C₆₀ solutions in good solvents are considered.     

Vibrational spectra of 2-cyclooctylamino-5-nitropyridine and its mixtures with C<Subscript>60</Subscript> and C<Subscript>70</Subscript> fullerenes

The vibrational spectra of 2-cyclooctylamino-5-nitropyridine (COANP) solutions and the evolution of the spectra upon changing over from the solutions to solid-phase COANP are investigated. The bands observed in the spectra are assigned to the corresponding vibrational modes. The nature of the interaction of COANP with C₆₀ and C₇₀ fullerenes is elucidated by analyzing the transmission spectra of these compounds. No interaction of the COANP compound with C₆₀ and C₇₀ fullerenes is revealed under the studied conditions. It is assumed that the physical nature of this phenomenon can be associated with the formation of liquid-crystal clusters consisting of fullerene molecules.     

Effect of fullerenes C60and C70 on the absorption spectrum of 2-cyclooctylamino-5-nitropyridine

The influence of fullerenes C₆₀ and C₇₀ on the absorption spectrum of 2-cyclooctylamino-5-nitropyridine (COANP) is studied. A substantial shift of the absorption band edge of COANP-C₇₀ to the IR region was observed. This effect was compared with the data obtained for COANP-C₆₀. The experimental results were explained using the model that takes into account the interaction between electronic subsystems of COANP and fullerene.     

A comparative study of ion-induced damages in C60 and C70 fullerenes

The stability of fullerenes (C₆₀ and C₇₀) under swift heavy ion irradiation is investigated. C₆₀ and C₇₀ thin films were irradiated with 120 MeV Ag ions at fluences from 1×10¹² to 3×10¹³ ions/cm². The damage cross-section and radius of damaged cylindrical zone were found to be higher for C₆₀ than C₇₀ as evaluated by Raman spectroscopy, which shows that the C₇₀ molecule is more stable under energetic ion impact. The higher damage cross-section of the C₆₀ molecule compared with that of the C₇₀ molecule is explained on the basis of thermal conductivity in the framework of the thermal spike model. The surface morphology of pristine C₆₀ and C₇₀ films is studied by atomic force microscopy. UV-visible absorption studies revealed that band gap for C₆₀ and C₇₀ fullerenes thin films decreases with increasing ion fluence. Resistivity of C₆₀ and C₇₀ thin films decreases with increasing ion fluence but the decrease is faster for C₆₀ than C₇₀, indicating higher damage in C₆₀. Irradiation at a fluence of 3×10¹³ ions/cm² results in complete damage of fullerenes (C₆₀ and C₇₀) into amorphous carbon.     

Adsorption of helium on isolated C60 and C70 anions

Adsorption of helium on free, negatively charged fullerenes is studied in this work. Helium nanodroplets have been doped with fullerenes and ionised by electron attachment. For suitable experimental conditions, C^?₆₀ and C^?₇₀ anions are found to be complexed with a large number of helium atoms. Prominent anomalies in the ion abundances indicate the high stability of the commensurate 1×1 phase in which all hollow adsorption sites are occupied by one atom each. The adsorption energy for an additional helium atom is about 40% less than for atoms in the commensurate layer, similar to our previous findings for fullerene cations and in agreement with theoretical dissociation energies. Similarly, an anomaly in the adsorption energy occurs when 60 helium atoms are attached to C^?₆₀ or 65 to C^?₇₀. For C₆₀, the anomaly coincides with the one observed for cationic complexes but for C₇₀ it does not. Implications of these features are discussed in light of several theoretical studies of neutral and positively charged helium–fullerene complexes.     

Atomic force microscopy of C60/C70 single-crystal fullerenes under ethanol

C₆₀/C₇₀ crystal surfaces were imaged by atomic force microscopy under ethanol with resolution of single molecules. Spherical and elongated elliptical fullerenes can be distinguished corresponding most likely with C₆₀, respectively C₇₀. Determination of the maximum diameter for a large number of molecules confirms the presence of two species of fullerenes, one with 9.4 Å, the other with 11.2 Å. The measured ratio C₆₀:C₇₀ is 81:19 which resembles the spectroscopical data. The molecules are arranged either in hexagonal (hcp) or cubic (fcc) packing, in some areas the two arrangements alternate within a few nm. Elongated fullerenes apparently prefer the hexagonal packing.     

Trapping intermediates and comparing relative reactivities: a DFT M06‐2X study on Diels–Alder cycloadditions of butadiene to C60 and C70

All possible types of Diels–Alder cycloadditions of 1,3‐cis‐butadiene to C₆₀ (2 in total) and to C₇₀ (8 in total) were theoretically investigated by the M06‐2X density functional method in gas phase and solutions. An intermediate between the reactant and the transition state was located for each reaction. These intermediates except one have not been experimentally or theoretically reported before. The reactivities of the 10 reactions in both the gas phase and solutions were systematically compared based on the calculated results. The present conclusion agrees with the experimental observations and partly disagrees with the previously theoretical conclusion. Copyright © 2012 John Wiley & Sons, Ltd.     

Formation of Zero Density Regions During the Dissolving of C60 and C70

Based on a comprehensive review of the calculated and experimental data obtained in this and previous articles by the authors, a phenomenological model of the supramolecular structure of fullerene solutions is proposed. The model suggests the development in the fullerene solutions of some zero density regions due to poor packing of spheroidal fullerene molecules C₆₀ and C₇₀, on the one hand, and columnar or ribbon supramolecular structures formed by solvent molecules, on the other. It is assumed that the source of the long-range energy of fullerenes is a physical vacuum, concentrated not only in the cavities of the fullerene molecules but also in new regions forming outside the fullerenes during their dissolving in single-ring aromatic solvents.     

Neutron scattering study of intermolecular excitations in solid C60 and C70

The spectrum of intermolecular excitations in solid C₆₀ and C₇₀ is investigated by neutron time-of-flight spectroscopy. The quasielastic scattering above the ordering transition is studied in detail and compared to a rotational diffusion model. Below the transition the scattering spectra have essentially a three peak structure with a prominent libronic excitation near ±2 meV for both fullerenes. A detailed analysis gives evidence for a broader distribution of librational modes with an additional pronounced maximum near 5 meV.     

Prediction of thermodynamic properties from pure compound information: Characterization of fullerenes

Fullerenes are widely studied not only in material, but also in life science due to their special properties. Their surface properties determine their interaction with the environment and influence adsorption as well as biodistribution. In this work, the surfaces of a series of fullerenes and polyhydroxylated C₆₀-fullerenes were investigated using density functional theory (DFT)/conductor-like screening model (COSMO)-calculations. The dependence of the screening charge density from the curvature of a carbon hexagon and its effect on the adsorption behavior was studied. The estimation of thermodynamic properties of multiply functionalized C₆₀-molecules gives promising qualitative results using only properties of the pure compounds.     

Buckminsterfullerene, higher fullerenes, and their endohedral and fluorine derivatives

This paper presents an overview of recent works concerned with determination of the electron affinity (EA) and the ionization energy (IE) for higher fullerenes and their endohedral and fluorine derivatives. The numerical values of the electron affinity are analyzed for higher fullerenes up to C₁₀₆ and lanthanum, gadolinium, and scandium endohedral fullerenes, including Sc₃N@C₈₀. Most attention is concentrated on two methods for producing fluorofullerenes, namely, direct fluorination of fullerenes with molecular fluorine in a manganese difluoride matrix and solid-phase reactions between fullerenes and fluorinating agents capable of donating fluorine to fullerene. The structures of three fluorofullerenes (C₆₀F₁₈, C₆₀F₂₀, and C₆₀F₄₈) characterized by a distortion of the carbon cage due to attachment of functional groups are discussed.     

Hybrid materials with an increased resistance to hard X‐rays using fullerenes as radical sponges

The protection of organic and hybrid organic–inorganic materials from X‐ray damage is a fundamental technological issue for broadening the range of applications of these materials. In the present article it is shown that doping hybrid films with fullerenes C₆₀ gives a significant reduction of damage upon exposure to hard X‐rays generated by a synchrotron source. At low X‐ray dose the fullerene molecules act as `radical scavengers', considerably reducing the degradation of organic species triggered by radical formation. At higher doses the gradual hydroxylation of the fullerenes converts C₆₀ into fullerol and a bleaching of the radical sinking properties is observed.     

Specific features of the formation of defects in fullerene C46

The initial stage of the formation of defects in the fullerene C₄₆ has been investigated using the atomistic computer simulation. It has been found that the relatively low symmetry of this fullerene leads to the emergence of channels of defect formation, which have not been revealed in the fullerenes C₂₀, C₃₆, and C₆₀. These channels consist in breaking a single C-C bond (in contrast to the simultaneous breaking of two bonds in the course of the Stone-Wales transformation, which is characteristic of high-symmetry fullerenes). For some typical channels, the paths of transformation of the C₄₆ fullerene into the corresponding defect isomers have been determined and the heights of the potential barriers encountered in these paths have been calculated.     

Determination of C60/C70 ratios in fullerene mixtures and film characterization by scanning tunneling microscopy

Fullerene powder mixtures with different C₆₀/C₇₀ ratios have been analyzed by a variety of techniques, and results have been compared. The fullerence mixtures have been characterized as solutions in n-hexane by high-pressure liquid chromatography (HPLC) and UV-VIS spectroscopy. Thin films of fullerenes on Au(111) have been prepared from the mixtures by sublimation. The sublimation process has been studied by simultaneous thermogravimetric and differential thermal analyses. Thin fullerene films on Au(111) have been investigated by scanning tunneling microscopy (STM). The STM images show primarily two types of ballshaped molecules arranged in a lattice with hexagonal symmetry (fcc(111) face, nearest neighbour distance: 1 nm). The two species differ in diameter. STM images of films made of mixtures of different C₆₀/C₇₀ ratios show that C₇₀ molecules display a larger apparent diameter (0.8 nm) and corrugation than C₆₀ molecules (0.7 nm). The C₆₀/C₇₀ ratios obtained by counting the corresponding molecular species in the STM images of the thin films are compared to the C₆₀/C₇₀ ratios determined by HPLC on hexane solutions of the mixtures. The observed differences might be explained by different rates of sublimation for the two species. The STM images reveal film defects (vacancies and boundaries) and dynamic processes (displacement of C₇₀ molecules and vacancies). In films prepared to have a C₆₀ coverage of less than one monolayer, stable structural units of the C₆₀(111) surface consisting of three or seven C₆₀ molecules are revealed by STM. Occasionally, substructure within individual fullerene molecules is observed.     

Investigations of the structure and conformations of star-shaped polymers with fullerene branching centers functionalized by carbonyl groups

Star-shaped polystyrenes (PS)₆C₆₀ in deuterated toluene, in which the surface of the fullerene C₆₀ center is modified by the attachment of one to three polar C=O groups, have been studied using small-angle neutron scattering. It has been found that a decrease in the concentration of solutions (from 1.0 to 0.1 g/dL) leads to a change in the local conformation of the arms on scales R ～ 1/q ≤ 1 nm from coiled to straightened fragments. The effect is enhanced in the presence of one or two C=O groups on the surface of the fullerenes. The results have been discussed in terms of the influence of fullerenes on the structure of the solvent.     

Longitudinal field repolarization studies of reorientational dynamics in the fullerenes C60 and C70

LFμSR studies on the pure fullerenes C₆₀ and C₇₀ show temperature dependent features associated with the reorientational behaviour of the fullerenyl radicals MuC₆₀ and MuC₇₀ in the crystalline host substrate. If not excluded from the experimental setup, molecular oxygen undergoes spin exchange reactions with the radicals. The data for C₆₀ correspond to a situation effectively static at 150 K and fully averaged to isotropy at 300 K, while for C₇₀ the data conspicuously do not conform to the predictions of the pseudostatic model employed in ALC‐μSR studies. This revised version was published online in August 2006 with corrections to the Cover Date.     

Radiation-stimulated modification of C60 films on Si-oxide surfaces

The electronic structure of C₆₀/SiO_x/Si(1 0 0) interface was studied by photoemission (valence-bands, C 1s, and Si 2p core levels) and near-edge X-ray absorption fine structure (C 1s threshold) spectroscopies. It was concluded that the SiO_x/Si surface is non-reactive with respect to the interaction with C₆₀. The exposure of the C₆₀/SiO_x/Si system under non-monochromatic synchrotron radiation causes modification of the electronic structure of this system. It is explained by polymerization of the C₆₀ molecules and arising a strong ionic-like interaction of the polymerized C₆₀ with the SiO_x surface. Annealing of this system up to temperatures of 550–625 °C leads to complete desorption of the C₆₀ molecules from the non-irradiated sample areas while the modified by radiation fullerenes remain attached to the substrate.