Annealing c60+: synthesis of fullerenes and large carbon rings

Laser vaporization of graphite generates C(60)(+) cluster ions that are fullerenes and a mixture of roughly planar polycyclic polyyne ring isomers. Experimental studies of the annealing of the non-fullerene C(60)(+) ions indicate that they can be converted (in the gas phase) into the fullerene and an isomer that appears to be a large monocyclic ring. Some fragmentation is associated with conversion to the fullerene geometry, but the majority of the non-fullerene C(60)(+) isomers are cleanly converted into an intact fullerene. The emergence of the monocyclic ring (as the clusters are annealed) suggests that this is a relatively stable non-spheroidal form of these all carbon molecules. The estimated activation energies for the observed structural interconversions are relatively low, suggesting that these processes may play an important role in the synthesis of spheroidal fullerenes.     

Radical reactions of c60

Photochemically generated benzyl radicals react with C(60) producing radical and nonradical adducts Rn C(60) (R = C(6)H(5)CH(2)) with n = 1 to at least 15. The radical adducts with n = 3 and 5 are stable above 50 degrees C and have been identified by electron spin resonance (ESR) spectroscopy as the allylic R(3)C(60)(.) (3) and cyclopentadienyl R(5)C(60)(.) (5) radicals. The unpaired electrons are highly localized on the C(60) surface. The extraordinary stability of these radicals can be attributed to the steric protection of the surface radical sites by the surrounding benzyl substituents. Photochemically generated methyl radicals also add readily to C(60). Mass spectrometric analyses show the formation of (CH(3))nC(60) with n = 1 to at least 34.     

Compressibility of solid c60

Room-temperature powder x-ray diffraction profiles have been obtained at hydrostatic pressures P = 0 and 1.2 gigapascals on the solid phase of cubic C(60) ("fullerite"). Within experimental error, the linear compressibility d(ln a)/dP is the same as the interlayer compressibility d(ln c)/dP of hexagonal graphite, consistent with van der Waals intermolecular bonding. The volume compressibility -d(ln V)/dP is 7.0 +/- 1 x 10(-12) square centimeter per dyne, 3 and 40 times the values for graphite and diamond, respectively.     

Fabrication and properties of free-standing c60 membranes

Van der Waals forces that bind C(60) molecular solids are found to be sufficiently strong to allow the reproducible fabrication of free-standing C(60) membranes on (100) silicon wafers. Membranes, 2000 to 6000 angstroms thick, were fabricated by a modified silicon micro-machining process and were found to be smooth, flat, and mechanically robust. An important aspect of the silicon-compatible fabrication procedure is the demonstration that C(60) films can be uniformly and nondestructively thinned in a CF(4) plasma. Young's modulus and fracture strength measurements were made on membranes with areas larger than 6 millimeters by 6 millimeters. It may be possible to use C(60), membranes for physical property measurements and applications.     

Crystal structure of osmylated c60: confirmation of the soccer ball framework

An x-ray crystal structure that confirms the soccer ball-shaped carbon framework of C(60) (buckminsterfullerene) is reported. An osmyl unit was added to C(60) in order to break its pseudospherical symmetry and give an ordered crystal. The crystal structure of this derivative, C(60)(OsO(4))(4-tert-butylpyridine)(2), reveals atomic positions within the carbon cluster.     

A rational chemical synthesis of C60

Isolable quantities of C60, the smallest stable fullerene, have been synthesized in 12 steps from commercially available starting materials by rational chemical methods. A molecular polycyclic aromatic precursor bearing chlorine substituents at key positions forms C60 when subjected to flash vacuum pyrolysis at 1100 degrees C. No other fullerenes are formed as by-products. The methods we have developed for the target-specific synthesis of fullerenes, applied here to a synthesis of C60, should make possible the directed laboratory preparation of other fullerenes as well, including those not accessible by graphite vaporization.     

Electrical resistivity and stoichiometry of kkhgr c60 films

Electrical resistances of polycrystalline fullerene (C(60)) films were monitored while the films were being doped in ultrahigh vacuum with potassium from a molecular-beam effusion source. Temperature- and concentration-dependent resistivities of K(chi) C(60) films in equilibrium near room temperature were measured. The resistance changes smoothly from metallic at chi approximately 3 to activated as chi --> = 0 or chi --> 6. The minimum resistivity for K(3)C(60) films is 2.2 microohm-centimeters, near the Mott limit. The resistivities are interpreted in terms of a granular microstructure where K(3)C(60) regions form nonpercolating grains, except perhaps at chi approximately 3. Stoichiometries at the resistivity extrema were determined by ex situ Rutherford backscattering spectrometry to be chi = 3 +/- 0.05 at the resistance minimum and chi = 6 +/- 0.05 at the fully doped resistance maximum.     

New phases of c60 synthesized at high pressure

The fullerene C(60) can be converted into two different structures by high pressure and temperature. They are metastable and revert to pristine C(60) on reheating to 300 degrees C at ambient pressure. For synthesis temperatures between 300 degrees and 400 degrees C and pressures of 5 gigapascals, a nominal face-centered-cubic structure is produced with a lattice parameter a(o) = 13.6 angstroms. When treated at 500 degrees to 800 degrees C at the same pressure, C(60) transforms into a rhombohedral structure with hexagonal lattice parameters of a(o) = 9.22 angstroms and c(o) = 24.6 angstroms. The intermolecular distance is small enough that a chemical bond can form, in accord with the reduced solubility of the pressure-induced phases. Infrared, Raman, and nuclear magnetic resonance studies show a drastic reduction of icosahedral symmetry, as might occur if the C(60) molecules are linked.     

Sled-type motion on the nanometer scale: determination of dissipation and cohesive energies of c60

The tribological properties of C(60) on the mesoscopic scale were investigated with a scanning force microscope, which allowed simultaneous measurements of normal and lateral forces under ultrahigh-vacuum conditions. Islands of C(60), deposited on NaCl(001), could be moved by the action of the probing tip in a controlled way. Different modes of motion, such as translation and rotation, were observed. An extremely small dissipation energy of about 0.25 millielectron volt per molecule and a cohesive energy of 1.5 electron volts were determined in these nanometer-scale experiments. The corresponding shear strength of 0.05 to 0.1 megapascal was smaller by one order of magnitude than typical values of boundary lubricants. For C(60) on graphite, disruption of the islands was observed and collective motion of the islands could not be achieved. These results could find use in the field of nanotechnology; for example, C(60) islands could be developed into a sled-type transport system on the nanometer scale.     

Existence of an orientational electric dipolar response in c60 single crystals

The dielectric constant in and conductivity sigma of undoped C(60) single crystals have been measured as a function of temperature, 10 K < T < 330 K, and frequency, 0.2 kilohertz < f < 100 kilohertz. On cooling below the first-order structural phase transition at 260 K, a Debye-like relaxational contribution to the dielectric response is observed, which requires the presence of permanent electric dipoles. The relaxation rate is thermally activated with a broad distribution of energies centered at 270 millielectron volts. The existence of a dipole moment in C(60) is unexpected, because it is precluded by symmetry for the pure ordered cubic phase. These data suggest that the high degree of frozen-in orientational disorder of the C(60) molecules is responsible for the existence of electric dipolar activity.     

The structure of the c60 molecule: x-ray crystal structure determination of a twin at 110 k

Single-crystal x-ray diffraction methods were used to determine the crystal and molecular structure of C(60) buckminsterfullerene. At 110 kelvin C(60) is cubic, apparent Laue symmetry m3m, but it exhibits noncrystallographic systematic extinctions indicative of a twin in which I(hkl) and I(khl) are superimposed. In fact, C(60) crystallizes with four molecules in space group [See equation in the PDF file] of the cubic system (Laue symmetry m3) with lattice constant a = 14.052(5) angstroms (A) at 110 kelvin. The twin components are equal. A given component, which has crystallographically imposed symmetry [See equation in the PDF file] displays an ordered structure of a truncated icosahedron. The five independent C=C bonds that join C(6) rings average 1.355(9) A; the ten independent C-C bonds that join C(6) and C(5) rings average 1.467(21) A. The mean atom-to-atom diameter of the C(60) molecule is 7.065(3) A. The molecules are very tightly packed in the crystal structure, with intermolecular C...C distances as short as 3.131(7) A.     

Encapsulation of molecular hydrogen in fullerene C60 by organic synthesis

In spite of their importance in fundamental and applied studies, the preparation of endohedral fullerenes has relied on difficult-to-control physical methods. We report a four-step organic reaction that completely closes a 13-membered ring orifice of an open-cage fullerene. This process can be used to synthesize a fullerene C60 encapsulating molecular hydrogen, which can be isolated as a pure product. This molecular surgical method should make possible the preparation of a series of C60 fullerenes, encapsulating either small atoms or molecules, that are not accessible by conventional physical methods.     

Bond lengths in free molecules of buckminsterfullerene, c60, from gas-phase electron diffraction

Electron diffraction patterns of the fullerene C(60) in the gaseous state have been obtained by volatilizing it from a newly designed oven-nozzle at 730 degrees C. The many peaks of the experimental radial distribution curve calculated from the scattered intensity are completely consistent with icosahedral symmetry for the free molecule. On the basis of this symmetry assumption, least-squares refinement of a model incorporating all possible interatomic distances led to the values r(g)(C(1)-C(2)) = 1.458(6) angstroms (A) for the thermal average bond length within the five-member ring (that is, for the bond fusing five- and six-member rings) and r(g)(C(1)-C(6)) = 1.401(10) A for that connecting five-member rings (the bond fusing six-member rings). The weighted average of the two bond lengths and the difference between them are the values 1.439(2) A and 0.057(6) A, respectively. The diameter of the icosahedral sphere is 7.113(10) A. The uncertainties in parentheses are estimated 2sigma values.     

C_(60)-D-氨基葡萄糖衍生物的制备及其抗氧化性的研究

在非均相碱性体系中,合成了C60-D-氨基葡萄糖衍生物,用FT-IR和1HNMR对产物的结构进行了表征。考察了C60-D-氨基葡萄糖衍生物的超氧阴离子清除能力、羟基自由基清除能力、还原能力以及金属螯合能力。结果表明:C60-氨基葡萄糖衍生物对超氧阴离子自由基O2-.和羟基自由基.OH的半抑制浓度分别是0.42mg/mL和0.26mg/mL;在还原能力体系中当吸光度达到0.5时,所需C60-D-氨基葡萄糖衍生物的浓度是2.44mg/mL;在金属螯合能力体系中,C60-D-氨基葡萄糖衍生物对亚铁离子的半螯合浓度是0.013mg/mL;即表明C60-D-氨基葡萄糖衍生物在4个抗氧化体系中都表现出明显的抗氧化性。并且D-氨基葡萄糖盐酸盐在4个体系中表现出的抗氧化能力都不强,说明C60-D-氨基葡萄糖衍生物的抗氧化能力可能主要来自于C60上保留下来的双键。     

Actinomycin D: inhibition of protein synthesis unrelated to effect on template RNA synthesis

Incubation of sarcoma-37 ascites cells in vitro with actinomycin D resulted in inhibition of synthesis of nuclear and cytoplasmic proteins. The overall inhibition could be prevented or relieved by glucose; it is thus unrelated to breakdown of template RNA.     

Stable compounds of helium and neon: he@c60 and ne@c60

It is demonstrated that fullerenes, prepared via the standard method (an arc between graphite electrodes in a partial pressure of helium), on heating to high temperatures release (4)He and (3)He. The amount corresponds to one (4)He for every 880,000 fullerene molecules. The (3)He/(4)He isotopic ratio is that of tank helium rather than that of atmospheric helium. These results convincingly show that the helium is inside and that there is no exchange with the atmosphere. The amount found corresponds with a prediction from a simple model based on the expected volume of the cavity. In addition, the temperature dependence for the release of helium implies a barrier about 80 kilocalories per mole. This is much lower than the barrier expected from theory for helium passing through one of the rings in the intact structure. Amechanism involving reversibly breaking one or more bonds to temporarily open a "window" in the cage is proposed. A predicted consequence of this mechanism is the incorporation of other gases while the "window" is open. This was demonstrated through the incorporation of (3)He and neon by heating fullerene in their presence.     

C_(60)-D-氨基葡萄糖衍生物的制备及其抗氧化性的研究

在非均相碱性体系中,合成了C60-D-氨基葡萄糖衍生物,用FT-IR和1HNMR对产物的结构进行了表征。考察了C60-D-氨基葡萄糖衍生物的超氧阴离子清除能力、羟基自由基清除能力、还原能力以及金属螯合能力。结果表明:C60-氨基葡萄糖衍生物对超氧阴离子自由基O2-.和羟基自由基.OH的半抑制浓度分别是0.42mg/mL和0.26mg/mL;在还原能力体系中当吸光度达到0.5时,所需C60-D-氨基葡萄糖衍生物的浓度是2.44mg/mL;在金属螯合能力体系中,C60-D-氨基葡萄糖衍生物对亚铁离子的半螯合浓度是0.013mg/mL;即表明C60-D-氨基葡萄糖衍生物在4个抗氧化体系中都表现出明显的抗氧化性。并且D-氨基葡萄糖盐酸盐在4个体系中表现出的抗氧化能力都不强,说明C60-D-氨基葡萄糖衍生物的抗氧化能力可能主要来自于C60上保留下来的双键。     

C60H2: Synthesis of the Simplest C60 Hydrocarbon Derivative

The reaction of C(60) with BH(3): tetrahydrofuran in toluene followed by hydrolysis yielded C(60)H(2). This product was separated by high-performance liquid chromatography and characterized as the addition product of H(2) to a 6,6-ring fusion (1alb isomer). The (1)H nuclear magnetic resonance (NMR) spectrum of the product remained a sharp singlet between -80 degrees and +100 degrees C, which suggests a static structure on the NMR time scale. Hydrolysis of the proposed borane addition product with acetic acid-d(1) or D(2)O yielded C(60)HD, and its (3)J(HD) coupling constant is consistent with vicinal addition. The observation of a single C(60)H(2) isomer is in complete agreement with earlier calculations that indicated that at most 2 of the 23 possible isomers of C(60) would be observable at equilibrium at room temperature. These results suggest that organoborane chemistry may be applied to further functionalization of fullerenes.