Thermionic emission from fullerenes

We investigate the time dependence of carbon cluster ions, formed via thermionic emission from photoexcited fullerenes (C₆₀ and C₇₀). By pulsing the extraction field, we are able to observe delayed ions formed as late as 100 µs after excitation at 532 nm, 355 nm, or 266 nm. All even-sized clusters in the range 36 n 70 undergo thermionic emission.     

Thermionic emission from the fullerenes

Delayed ionisation of the fullerenes is reported over a timescale of up to 16 µs and compared to the Klots' model for thermionic emission [1]. The laser fluence dependence of the observed time constants for ionisation and the measured dependence on cluster size are in good agreement with model predictions giving strong evidence for the thermionic nature of the ionisation process.     

Anisotropic hot electron emission from fullerenes

Photoelectron spectra for fullerenes C(60) and C(70) ionized using 800 nm laser pulses with pulse durations from 120 to 1000 fs show thermal electron kinetic energy distributions but they also exhibit angular anisotropy with respect to the laser light polarization. The effective temperature of electrons, measured along the laser polarization direction, is significantly higher than in the perpendicular direction. We explain this observation by considering that the emission of the thermal electrons is uncorrelated with the phase of the laser pulse, unlike directly ionized electrons, and, depending on the time of emission, they may experience an additional "kick" from the vector potential of the laser field when they are emitted from the molecule.     

High performance liquid chromatographic–mass spectrometric detection of giant fullerenes

Fullerene-rich soot generated by resistive heating of graphite has been gently extracted with toluene, in order to remove some C₆₀ and C₇₀ compounds, followed by extraction with boiling 1,2,4-trichlorobenzene at 214°C. After filtration and removal of the solvent, the residue was re-dissolved in dichloromethane and characterized by non-aqueous reversed phase liquid chromatography coupled on-line with atmospheric pressure chemical ionization mass spectrometry. Several novel fullerenes were detected, including C₇₂, C₈₀, C₈₆, and C₈₈ as well as other fullerenes up to C₁₀₈ and higher. The results indicate that chromatographic separation of large fullerene molecules can be achieved with low boiling point solvents and conventional liquid chromatographic techniques.     

Three-stage transformation pathway from nanodiamonds to fullerenes

The dynamics of structure evolution of nanodiamonds ranging from 22 to 318 atoms of various shapes is studied by density functional tight-binding molecular dynamics. The spherical and cubic nanodiamonds can be transformed into fullerene-like structures upon heating. A number of the transformed fullerenes consist of pentagons and hexagons only. Others contain squares, heptagons, and octagons. One simulated fullerene is an isomer of C(60). The temperature of the transformation depends on the size, shape, and orientation of initial cluster. To be transformed into onion-like fullerenes, the spherical nanodiamonds should have 200 atoms or more, while the cubic ones require 302 atoms or more. The time-resolved energy profiles of all the transformations clearly reveal three-stage transformation character. During the first stage, the energy reduces quickly due to converting sp(3) carbon with dangling bond at the surface into sp(2) one, and the formation of partial sp(2) envelope wrapping the cluster. For the second stage, energy decreases slowly. The remaining interior carbon atoms come to the surface through the hole in the sp(2) envelope, and similar amount of sp(3) and sp(2) atoms coexist. The third stage involves the closure of holes, accompanied by the detachment of C(2) molecules and carbon chains from the edges. The energy decreases relatively fast in this stage. The proposed three-stage transformation pathway holds for all the simulations performed in this work, including those with the instant heating.     

Photodynamic release of fullerenes from within carbon nanohorn

We have found that oxidized single-wall carbon nanohorns (SWNHox) can exhibit a near-infrared (NIR) laser-triggered accelerated release of encapsulated fullerenes (C₆₀) from within their inner nanospaces. After the NIR laser irradiation of an aqueous SWNHox encapsulating C₆₀ solution/toluene biphasic system, C₆₀ molecules are enriched in the toluene phase. NIR laser-driven SWNHs encapsulating substrates could initiate the development of a new range of drug-delivery systems.     

Flattened fullerenes

Quantum-chemical calculations of giant flattened fullerenes C _n (lentil-shaped) have been carried out. The topology, molecular and electronic structure of these fullerenes have been studied. Such molecules consist of two identical coronenoid fragments of a graphite layer, which are arranged one above the other, and a system of polycondensed five- and six-membered cycles, which form a side surface of the cluster. Polyhedral structures with isolated pentagons of three symmetry types (D _6h ,D _6d , andD _3h ) have been considered. The topology of these structures is described in terms of planar molecular graphs. Electronic structures of eleven flattened lentil-shaped C _n clusters (n = 72–216) have been studied in the π approximation. Most of the considered systems have closed or quasi-closed electron shells (according to Hückel) and rather large energy gaps separating the highest occupied and lowest unoccupied MO, which is indicative of their kinetic stability. Fragments of the potential energy surfaces of the C₇₂ and C₉₆ fullerenes have been studied by the MNDO, AM1, and MNDO/PM3 methods. For the C₉₆ cluster, two local energy minima, which correspond to the lentil-shaped isomers withD _6h andD _6d symmetry, have been determined. As a result of optimization of geometric parameters, it was found that all three methods give close values of heights (H = 6.7 Å) and diameters (D = 9.8 Å) for both isomers. The clusters change to quasi-two-dimensional systems (H«D) with increasing sizes of coronenoid fragments.     

Transmutation of fullerenes

Fullerenes were pyrolyzed by subliming them into a stream of flowing argon gas and then passing them through an oven heated to approximately 1000 degrees C. C(76), C(78), and C(84) all readily lost carbons to form smaller fullerenes. In the case of C(78), some isomerization was seen. Pyrolysis of (3)He@C(76) showed that all or most of the (3)He was lost during the decomposition. C(60) passes through the apparatus with no decomposition and no loss of helium.     

碳笼化学 1

本文介绍并评述了碳笼化学的最新进展, 指出这是一个前景十分诱人的现代化学新兴领域。     

Aggregates of polymer-substituted fullerenes

We analyzed the self-organized supermolecular architectures observed in solutions of singly polymer-substituted fullerenes by light-scattering and fluorescence spectroscopy, as well as the surface pattern obtained from spraying the solution by atomic force microscopy. We found that the concentration dependence on aggregate size and fluorescence intensity can be explained quantitatively using a scaling argument, assuming that the aggregates in solution are self-emulsified micelles. Our results indicate that the core of the structure is unreacted fullerenes. Based on our scaling arguments, we predict that there is a critical molecular weight that allows for a narrow distribution of the self-assembled structures in solution.     

内嵌富勒烯的研究进展

内嵌富勒烯由于其结构新颖以及独特而优异的性质在国际上引起持续而广泛的关注,成为近年来的研究热点之一.目前已经研究发现的内嵌富勒烯多达近百种,从惰性气体到碱土金属再到稀土元素都已被成功地嵌入到不同尺寸的碳笼中.其中金属离子或含金属的离子簇内嵌入富勒烯碳笼形成的内嵌金属富勒烯,以其种类丰富、结构多样成为内嵌富勒烯的主要研究对象.本文就近年来研究报道的种类繁多的内嵌富勒烯按其内嵌物类型进行归纳阐述,为今后开发更多新型的内嵌富勒烯提供一定的参考.     

Classification system for fullerenes

The universal classification of nanoshells developed on the basis of group theory makes it possible to formulate new rules of the composition and structure of fullerenes. The classification shows the possible numbers of atoms for a given point group of symmetry, their arrangement at the symmetry elements, the number of nonequivalent groups of atoms in a structure, their coordination numbers, and the angles between bonds. The suggested formulas of the compositions of nanostructures and their classification is valid for all fullerenes known thus far and makes it possible to determine the compositions of as yet unknown fullerenes. The composition of heteroatomic nanoparticles with differently coordinated atoms composed of several shells shifted with respect to one another in accordance with the lengths and angles of chemical bonds between atoms of these shells can also be determined. The suggested procedure was used for calculating bridging diatomic nanostructures, for which a general formula for determining the compositions is derived. The stability of some predicted structures is supported by accurate quantum-chemical calculations.     

Aromaticity of corazulenic fullerenes

A novel class of non-classical fullerenes, having pentagon–heptagon pairs, as in azulene, is modeled. The various coverings, sometimes alternating azulenic and benzenic units, are designed by some new sequences of map operations or generalized operations. The hypothetical azulenic fullerenes are characterized by PM3 semiempirical data and POAV1 strain energy SE. Their aromaticity is discussed in the light of several criteria. The HOMA index of aromaticity enabled evaluation of global and local aromaticity of the designed fullerenes.     

Strain in Platonic fullerenes

Platonic fullerenes are those structures, either closed or open ones, covered by a single type of polygonal face. Excepting the graphite sheet, all the other nano-structures show non-zero strain energy. In this study, Platonic nanostructures, covered by polygonal faces f _k , k = 5–7, are designed and optimized at Hartree–Fock HF and DFT levels of theory. Next, their stability, in terms of total energy and HOMO–LUMO gap, strain energy (by POAV theory), HOMA index of aromaticity, and Kekulé structure count, is discussed. Vibrational spectra for the open fullerenes are also given.     

Transition metal coated fullerenes

Compound clusters of fullerene molecules and transition metal atoms having the composition C₆₀M_x and C₇₀M_x with x = 0..150 and M ∈ {Ti, Zr, V, Y, Ta, Nb} were produced using laser vaporisation in a low-pressure inert gas aggregation cell. Intensity anomalies in the mass spectra correlate with the atomic radii of the different metals indicating the formation of complete metal layers around the central fullerene molecule. Using high laser intensities the metal-fullerene clusters can be transformed into metcars and metal-carbides. Photofragmentation spectra of preselected C₆₀Ta_x indicate that the fullerene cage is destroyed for x ≥ 3.     

Mass spectrometry and fullerenes

This article presents, from amass spectrometry perspective, an historical account of research on gas-phase carbon clusters, which has led to the discovery of another form of carbon, fullerenes. In addition, more recent mass spectrometric studies on analysis of fullerene derivatives and synthesis of doped fullerenes are described. The early, strong evidence for certain “magic number” carbon clusters, most notably C₆₀ (buckminsterfullerene), was obtained largely from mass spectrometric experiments. These studies led to the controversial postulation of the soccerball structure for C₆₀, which provoked increased experimental and theoretical efforts. This research eventually resulted in the discovery of a simple method by which large quantities of fullerenes can be produced. The availability of these new, all-carbon molecules has motivated a broad range of synthetic and characterization studies that are expanding at a frenetic pace. Mass spectrometry not only played a critical role in the discovery of fullerenes but also now is crucial for determination of the unusual chemical and physical properties of fullerenes and fullerene-based materials.     

Why fluorinate fullerenes?

This review explores the reasons for fluorinating fullerenes, describes mechanistic deductions from studies carried out to date, explores future directions, and evaluates applications to large-scale preparative chemistry. Some previous structural characterisations are updated in the light of more recent data and interpretations.