Simulating the thermal behavior and fragmentation mechanisms of exohedral and substitutional silicon-doped C60

Structures, thermal behavior, and fragmentation mechanisms of exohedral and substitutional silicon-doped C(60) containing 1-12 Si atoms are investigated by extensive molecular-dynamics simulations. A nonorthogonal tight-binding model is used to mimic the interatomic interactions in the doped fullerenes. Beginning from the minimum-energy structures, the temperature of the doped fullerenes is slowly increased until fragmentation takes place. A correlation can be established between the exohedral and substitutional structures and the corresponding fragmentation mechanisms and fragmentation temperatures. Exohedral C(60)Si(m) fullerenes fragment into two homonuclear pieces, the Si(m) cluster and the C(60) fullerene that remains intact. In contrast, the substitutional C(60-m)Si(m) heterofullerenes undergo structural transformations, including the partial unraveling of the cage, prior to fragmentation. Then, ejection of atoms or small molecules takes place from the distorted structures. The slow heating rate used, combined with long simulation runs, allows us to determine the fragmentation temperature of exohedral and substitutional Si-doped fullerenes as a function of the number of silicon atoms. Substitutional Si-doped fullerenes exhibit much higher fragmentation temperatures (1000-1500 K higher) than the exohedral fullerenes. This can be understood from the different bonding of the Si atoms in both structures.     

Selective extraction of higher fullerenes using cyclic dimers of zinc porphyrins

Higher fullerenes (>/=C76) were selectively extracted from a fullerene mixture obtained from a combustion-based industrial production source by cyclic dimers of beta-unsubstituted porphyrin zinc complexes 2C5-2C7 with C5-C7 alkylene spacers as host molecules. Results of single extraction of the fullerene mixture with 2C5-2C7 together with a beta-substituted analogue of 2C6 (1C6) and spectroscopic titration of 2C6 and 1C6 with C60, C70, and C96 indicated that the host selectivity toward higher fullerenes is much dependent on the structure of the porphyrin units and the size of the host cavity. Sequential three-stage extraction of the fullerene mixture with the best-behaved 2C6 resulted in considerable enrichment in very rare fullerenes C102-C110 (<0.1 abs %) up to 82 abs % (C76-C114, 99 abs %) (356 nm) of total fullerenes.     

Synthesis of C59Hx and C58Hx fullerenes stabilized by hydrogen

Prolonged hydrogenation of C(60) molecules by reaction with H(2) at elevated temperature and pressure results in fragmentation and collapse of the fullerene cage structure. However, fragments can be preserved by immediate termination of dangling bonds by hydrogen. Here we demonstrate that not only fullerene fragments but also hydrogenated fragmented fullerenes (e.g., C(58)H(40) and C(59)H(40)) can be synthesized in bulk amount by high-temperature hydrogenation of C(60). We confirm successful synthesis of these species by matrix-assisted laser desorption ionization time-of-flight mass spectrometry and complete speciation of the resultant complex fullerene mixtures by high-resolution field desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry.     

Theoretical study of endohedral C36 and its dimers

It is found that atoms of lithium and carbon can be encapsulated in C(36) on the basis of the calculation of their encapsulation energies using density functional theory. Specifically, they can be encapsulated in C(36) better than in C(60) despite the smaller (70%) cavity size of the former. In C@C(36), the encapsulated carbon atom forms covalent bonds with the carbon atoms of the cage, which is in contrast with the case of N@C(60.) Two isomers are expected to be in an equilibrium which involves spin quenching and generation. Li@C(36) and C@C(36) are expected to exist in the form of dimers with nonendohedral fullerenes, i.e., as Li@C(36)-C(36) and C@C(36)-C(36). Three stable isomers were found for the former (A, B, and C). Equilibrium between A and C as well as that between B and C is accompanied by spin transfer between two fullerene units, while that between A and B is not. The two stable isomers in C@C(36)-C(36) form an equilibrium accompanied by spin quenching and generation, allowing the dimer to be potentially useful for molecular devices.     

DFT study of fullerene dimers.

Several [2+2] dimerization products of a fullerene Cn (n=50, 52, 54, 56, 58, 60) in its most stable form are presented and discussed. In total, 34 dimers are studied. Only symmetric Cn-Cn dimers (no mixed products) are reported, and only dimers of the fullerenes C50 to C58 with bonds between C atoms in adjacent pentagons are considered. Geometries were optimized within the framework of density functional theory using the Becke-Perdew exchange-correlation functional (BP86) in combination with an empirical dispersive energy correction, which contributes significantly to the binding energy. The results are discussed in the context of the reactivity of adjacent pentagon sites. The lateral interaction between fullerenes is found to be stronger for C50 to C58 than for C60, which is consistent with recent experimental observations. Further, the possibility of polymer formation based on the investigated [2+2] reaction is addressed.     

Effect of the cooling rate on dimerization of C60(•-) in fullerene salt (DMI+)2·(C60(•-))·{Cd(Et2NCS2)2I-}

The salt (DMI(+))(2)·(C(60)(?-))·{Cd(Et(2)NCS(2))(2)I(-)} (1) containing fullerene radical anions, the anions of cadmium diethyldithiocarbamate iodide, and N,N'-dimethylimidazolium cations was obtained. Fullerenes are monomeric in 1 at 250 K and form three-dimensional packing in which each fullerene has nearly tetrahedral surroundings from neighboring fullerenes. Fullerenes with a shorter interfullerene center-to-center distance of 10.031(2) ? form spiral chains arranged along the lattice c axis. The convolution consists of four fullerene molecules. Dimerization realized in 1 within the spiral chains below 135 K manifests a strong dependence on the cooling rate. The "frozen" monomeric phase was obtained upon instant quenching of 1. This phase is stable below 95 K for a long time but slowly converted to the dimeric phase at T > 95 K. It exhibits a weak antiferromagnetic interaction of spins below 95 K (the Weiss temperature is -4 K), which results in the splitting of the electron paramagnetic resonance (EPR) signal into two components below 10 K. A disordered phase containing both C(60)(?-) monomers and singly bonded (C(60)(-))(2) dimers with approximately 0.5/0.5 occupancies is formed at an intermediate cooling rate (for 20 min). The position of each fullerene in this phase is split into three positions slightly shifted relative to each other. The central position corresponds to nonbonded fullerenes with interfullerene center-to-center distances of 9.94-10.00 ?. Two other positions are coincided to dimeric fullerenes formed with the right and left fullerene neighbors within the spiral chain. This intermediate phase is paramagnetic with nearly zero Weiss temperature due to isolation of C(60)(?-) by diamagnetic species and exhibits a strongly asymmetric EPR signal below 20 K. A diamagnetic phase containing ordered singly bonded (C(60)(-))(2) dimers can be obtained only upon slow cooling of the crystal for 6 h.     

C59Si on the monohydride Si(100):H-(2 x 1) surface

We propose the use of the Si atom in the experimentally observed C59Si molecule as a possible way to controllably anchor fullerene molecules on a Si surface, due to the formation of a strong bond to one of the Si surface atoms. All our results are based on ab initio total energy density functional theory, and we obtain that the binding energy is on the order of 2.1 eV, approximately 1.4 eV more stable than a C60 bonded in a similar situation. A possible route to obtain such adsorption via a (C59Si)2 dimer is examined, and we find the whole process to be exothermic by approximately 0.2 eV.     

Local modifications of single-wall carbon nanotubes induced by bond formation with encapsulated fullerenes

Defected fullerenes in nanopeapods form bonds with the encapsulating single-walled carbon nanotubes when irradiated by an electron beam leading to changes in the guest (fullerene) and the host (nanotube). Intrinsic reaction coordinate (IRC) analysis based on B3LYP hybrid density functional theory shows that a C1-C59 defect with a single protruding C atom is initially formed from the C60(Ih) cage. The high activation energy for this step (8.37 eV (193.0 kcal/mol)), being assumed to be accessible during irradiation, is lower than that of the Stone-Wales rearrangement on the sp2 network. The binding of the defected fullerene to the nanotube is preferential, orthogonal bonds relative to the tube axis being slightly preferred. Because of the covalent bonds formed between the guest and host, the carbon network on the nanotube is locally perturbed in the vicinity of the binding site. As a result of the new bonds, bisnorcaradiene-like as well as quinonoid-like patterns appear near the binding site. These results are interpreted using orbital interaction and Clar diagram arguments. The changes in the bonding pattern on the nanotube should be significant in further functionalization of carbon nanotubes.     

Stabilities of multiply charged dimers and clusters of fullerenes

The authors find even-odd variations as functions of r (...+[C60]2(r+)([C60C70](r+)) electron-transfer collisions. This even-odd behavior is in sharp contrast to the smooth one for fullerene monomers and may be related to even-odd effects in dimer ionization energies in agreement with results from an electrostatic model. The kinetic energy releases for dimer dissociations [predominantly yielding intact fullerenes [C60]2(r+)-->C60(r1+)+C60(r2+) in the same (r1=r2) or nearby (r1=r2+/-1) charge states] are found to be low in comparison with the corresponding model results indicating that internal excitations of the separating (intact) fullerenes are important. Experimental appearance sizes for the heavier clusters of fullerenes [C60]n(r+) (n>3 and r=2-5) compare well with predictions from a new nearest-neighbor model assuming that r unit charges in [C60]n(r+) are localized to r C60 molecules such that the Coulomb energy of the system is minimized. The system is then taken to be stable if (i) two (singly) charged C60 are not nearest neighbors and (ii) the r C60(+) molecules have binding energies to their neutral nearest neighbors which are larger than the repulsive energies for the (r-1) C60(+)-C60(+) pairs. Essential ingredients in the nearest-neighbor model are cluster geometries and the present results on dimer stabilities.     

Geometric and electronic structures of metal-substitutional fullerene C59Sm and metal-exohedral fullerenes C60Sm

The geometric and electronic structures of metal-substituted fullerene C59Sm and exohedral fullerenes C60Sm are studied using the density-functional theory. The geometric optimization shows that the replacement of a C atom with a Sm in C60 yields a stable substitutionally doped fullerene C59Sm, and among the five possible optimized geometries for C60Sm, the most favorable exohedral sites are above the center of a hexagon and a pentagon ring. The calculations for electronic structures show that the magnetic moment of Sm is preserved for all the stable structures as tiny hybridization takes place between the orbitals of the Sm atom and those of their neighboring carbons. Because of the small energy gaps and the half occupation of the highest occupied molecular orbitals, all the stable C60Sm isomers are inferred to be conductors.     

A DFT study on the dimerization of C62, H2-C62, and F2-C62

On the basis of calculations using the density functional theory, we show that C(62), a recently synthesized nonclassical fullerene, will presumably undergo dimerization with various isomers at elevated temperatures. This is shown by calculating the dimerization energy and the activation barrier of the dimerization. Eight possible isomers of the dimer were identified, all of which are more stable than the two isolated monomers. The relative stability of various isomers depends upon the kind of C=C bonds within the four-membered carbon ring involved in the dimerization. In addition, similar calculations were performed for the monomers and dimers of H(2)-C(62) and F(2)-C(62). Six isomers were identified for each of the dimers. Although less pronounced than the case of the C(62) dimer, all isomers of the H(2)-C(62) dimer are appreciably more stable than the individual monomers. Although a large steric repulsion due to F atoms significantly reduces the stability of F(2)-C(62) dimer, its two isomers are still more stable than separate monomers.     

Li4C60: a polymeric fulleride with a two-dimensional architecture and mixed interfullerene bonding motifs

All known fullerene polymers have interfullerene connections via either [2 + 2] cycloaddition or single C-C bonds. The high-resolution synchrotron X-ray powder diffraction technique was employed here to determine the crystal structure of the Li4C60 fulleride. We find that the ground state of Li4C60 is a two-dimensional polymer with monoclinic crystal symmetry and an unprecedented architecture, combining both the [2 + 2] cycloaddition and the single C-C bridging motifs. The small size of the Li+ cations is crucial in stabilizing the resulting tightly packed polymeric structure.     

M4 @Si28 (M=Al,Ga): metal-encapsulated tetrahedral silicon fullerene

It is known that silicon fullerenes cannot maintain perfect cage structures like carbon fullerenes. Previous density-functional theory calculations have shown that even with encapsulated species, nearly all endohedral silicon fullerenes exhibit highly puckered cage structures in comparison with their carbon counterparts. In this work, we present theoretical evidences that the tetrahedral fullerene cage Si(28) can be fully stabilized by encapsulating a tetrahedral metallic cluster (Al(4) or Ga(4)). To our knowledge, this is the first predicted endohedral silicon fullerene that can retain perfectly the same cage structure (without puckering) as the carbon fullerene counterpart (T(d)-C(28) fullerene). Density-functional theory calculations also suggest that the two endohedral metallosilicon fullerenes T(d)-M(4)@Si(28) (M=Al and Ga) can be chemically stable because both clusters have a large highest occupied molecular orbital-lowest unoccupied molecular orbital energy gap ( approximately 0.9 eV), strong spherical aromaticity (nucleus-independent chemical shift value of -36 and -44), and large binding and embedding energies.     

Incorporating C2 into C60 films

The material formed by depositing C(2)(-) anions onto/into thin C(60) films (on graphite) at room temperature has been studied by means of thermal desorption mass spectroscopy, ultraviolet photoionization spectroscopy, atomic force microscopy (AFM), and surface enhanced Raman spectroscopy. As-prepared, C(2)/C(60) films manifest thermal desorption behaviour which differs significantly from pure C(60) films. Whereas the latter can be fully sublimed, we observe decomposition of C(2)/C(60) films to a high-temperature-stable material while predominantly C(60), C(62), and C(64) are desorbed in parallel. Deposition of C(2)(-) also leads to significantly modified electronic and vibrational properties. Based on DFT model calculations of the Raman spectra, we suggest that as-prepared C(2)/C(60) films contain appreciable amounts of polymeric networks comprising -C(2)-C(60)-C(2)-C(60)- chains. Detection of sublimed C(62) and C(64) upon heating implies that thermal decomposition of C(2)/C(60) films involves addition/uptake of C(2) units into individual fullerene cages. Correspondingly, annealing films up to various intermediate temperatures results in significant modifications to valence-band UP spectra as well as to surface topographies as imaged by AFM. The novel carbonaceous material obtained by heating to T > 950 K has a finite density of states at the Fermi level in contrast to as-prepared C(2)/C(60). It comprises fused fullerene cages.     

Electrochemically formed fullerene-based polymeric films

The recent results of investigations involving the electrochemical formation of polymers containing fullerenes and studies of their properties and applications are critically reviewed. From a structural point of view, these polymers can be divided into four main categories including (1) polymers with fullerenes physically incorporated into the foreign polymeric network without forming covalent bonds, (2) fullerene homopolymers formed via [2+2] cycloaddition, (3) “pearl necklace” polymers with fullerenes mutually linked covalently to form polymer chains, and (4) “charm bracelet” polymers containing pendant fullerene substituents. The methods of electrochemical polymerization of these systems are described and assessed. The structural features and properties of the electrochemically prepared polymers and their chemically synthesized analogs are compared. Polymer films containing fullerenes are electroactive in the negative potential range due to electroreduction of the fullerene moieties. Related films made with fullerenes derivatized with electron-donating moieties as building blocks are electroactive in both the negative and positive potential range. These can be regarded as “double cables” as they exhibit both p- and n-doping properties. Fullerene-based polymers may find numerous applications. For instance, they can be used as charge-storage and energy-converting materials for batteries and photoactive units of photovoltaic cell devices, respectively. They can be also used as substrates for electrochemical sensors and biosensors. Films of the C₆₀/Pt and C₆₀/Pd polymers containing metallic nano-particles of platinum and palladium, respectively, effectively catalyze the hydrogenation of olefins and acetylenes. Laser ablation of electrochemically formed C₆₀/M and C₇₀/M polymer films (M=Pt or Ir) results in fragmentation of the fullerenes leading to the formation of hetero-fullerenes, such as [C₅₉M]⁺ and [C₆₉M]⁺.Dedicated to Professor Dr. Alan M. Bond on the occasion of his 60th birthday.     

Toward controlled spacing in one-dimensional molecular chains: alkyl-chain-functionalized fullerenes in carbon nanotubes

A range of fullerenes (C60) functionalized with long alkyl chains have been synthesized and inserted into single-walled carbon nanotubes. The impact of the alkyl chain length and of the type of linker between the addend and the fullerene cage on the geometry of molecular arrays in nanotube has been studied by high-resolution transmission electron microscopy. In the presence of functional groups the mean interfullerene separations are significantly increased by 2-8 nm depending on the length of the alkyl chain, but the periodicity of the fullerene arrays is disrupted due to the conformational flexibility of the alkyl groups.     

Approaches to open fullerenes: synthesis and thermal stability of cis-1 bis(isobenzofuran) Diels-Alder adducts of C60

In a quest to form wider openings within the cage of the fullerene C60 through controlled bond-breaking reactions, we have examined the double saturation of adjacent C=C bonds within a six-membered ring of C60. We have investigated the double Diels-Alder cycloaddition of two tethered isobenzofurans to the fullerene C60. We obtained cis-1 adducts in good yields after reacting the methylene- or quinoxaline-tethered bis(isobenzofuran) precursors 2a-k with parent 3,6-dihydro-1,2,4,5-tetrazine (3b). The X-ray structure of the methylene-tethered bis(isobenzofuran)-C60 adduct 4b has been obtained; four-eclipsed substituents are held rigidly by the bicyclic addends. The cis-1 bis(isobenzofuran) bisadducts 4b and 4e-j are kinetically far more stable toward thermal retro-Diels-Alder fragmentation than are mono(isobenzofuran) adducts of C60, in solution and in the solid state as determined by 1H NMR spectroscopy or thermogravimetric analysis. A methodology for the reversible solubilization of other fullerene derivatives based on this work is also presented.     

Ionic and neutral C60 complexes with coordination assemblies of metal tetraphenylporphyrins, MIITPP2.DMP (M=Mn, Zn). Coexistence of (C60-)2 dimers bonded by one and two single bonds in the same compound

Coordination assemblies of metal tetraphenylporphyrins, MIITPP2.DMP (M=Mn, Zn) were shown to form ionic multicomponent and neutral complexes with fullerene, {(MnIITPP)2.DMP}.(C60-)2.(DMETEP+)2.(C6H4Cl2)5 (1) and {(ZnTPP)2.DMP}.(C60)2.(C6H5Cl)4 (2), where DMP=N,N'-dimethylpiperazine and DMETEP+=the cation of N,N'-dimethyl-N'-ethylthioethylpiperazine. The crystal structure of 1 contains zigzag chains of the (C60-)2 dimers alternating with the DMETEP+ cations in the channels formed by the (MnIITPP)2.DMP units, whereas in 2 zigzag chains of the C60 molecules are separated by the (ZnTPP)2.DMP units and C6H5Cl molecules. The (MIITPP)2.DMP assemblies (M=Mn, Zn) have axial M-N(DMP) bonds of 2.315(2) and 2.250(2) A length, average equatorial M-N(DMP) bonds elongated to 2.141(3) and 2.077(2) A, and MII atoms displaced from the porphyrin plane toward the ligand by 0.677 and 0.485 A, respectively. The single-bonded sigma-(C60-)2 dimer coexists in 1 with the (C60-)2 dimer bonded by two single bonds with 86/14 occupancy factors. The sigma-(C60-)2 dimers are unusually stable and begin to dissociate only above a temperature of 320-330 K that results in the increase of the magnetic moment of 1 from 8.33 microB (320 K) to 8.66 microB (360 K). The electron paramagnetic resonance (EPR) signal of the dimeric phase (T<320 K) with the features spread over the range of 0-0.7 T was attributed to the interacting Mn2+ centers in the (MnIITPP)2.DMP units. The dissociation of the sigma-(C60-)2 dimers to the EPR-active C60*- radical anions manifests a new broad Lorenz signal above 320 K with g=2.0179 and DeltaH=65.5 mT. This signal can appear due to the exchange coupling between paramagnetic (MnIITPP)2.DMP and C60*- species. The vis-NIR spectrum of the sigma-(C60-)2 dimers is discussed.     

Cn films (n=50, 52, 54, 56, and 58) on graphite: cage size dependent electronic properties

Novel semiconducting materials have been prepared under ultrahigh-vacuum conditions by soft-landing mass-selected Cn+ (50< or =n<60; even n) on highly oriented pyrolytic graphite surfaces at mean kinetic energies of 6 eV. In all cases, Cn films grow according to the Volmer-Weber mechanism: the surface is initially decorated by two-dimensional fractal islands, which in later deposition stages become three-dimensional dendritic mounds. We infer that Cn aggregation is governed by reactive sites comprising adjacent pentagons (or heptagons) on individual cages. The resulting covalent cage-cage bonds are responsible for the unusually high thermal stability of the films compared to solid C60. The apparent activation energies for intact Cn sublimation range from 2.2 eV for C58 to 2.6 eV for C50 as derived from thermal desorption spectra. All Cn films exhibit a common valence-band ultraviolet photoelectron spectroscopy spectral feature located around the center of a broad highest occupied molecular-orbital (HOMO)-derived band (EB approximately 2.5 eV). This feature has been assigned to Cn units covalently linked to each other in polymeric structures. To within experimental accuracy, the same work function (4.8 eV) was determined for thick films of all Cn studied. In contrast, "HOMO" ionization potentials were cage size dependent and significantly lower than that obtained for C60. C58 exhibited the lowest HOMO (6.5 eV). Band gaps of Cn films have been determined by depositing small amounts of Cs atoms onto the topmost film layer. HOMO-lowest unoccupied molecular-orbital-derived band gaps between 0.8 eV (C52) and 1.8 eV (C50) were observed, compared to 1.5 eV for solid C60.     

DFT study on a fullerene doped with Si and N

DFT calculations are applied for some stable C₆₀, C₅₉Si, and C₅₉N hetero fullerenes. Sn and Ge atoms are doped at the same position of C₆₀. Computations are carried out at the B3LYP/cc pVDZ levels. In this work the effects of the heteroatoms, Si and N, on the structural properties of the fullerene have been studied. The structure, energetic and relative stabilities of the compounds were compared and analyzed with each other. In addition, vibrations spectra of proposed stable neutral species, as well as the infrared intensities are calculated. From the data obtained from calculation, we found that there is strong correlation between the stability of pure C₆₀ fullerene molecule and the numbers of different C-C bonds.