EPR spectra of C60 anions

The broad and sharp EPR signals observed in spectra of C₆₀ and C ₆₀ ^3? are summarized and proposed assignments are discussed. The sharp signals in samples of C ₆₀ ^2? are reviewed.     

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.     

Photoinduced C70 radical anions in polymer:fullerene blends

Photoinduced polarons in solid films of polymer:fullerene blends were studied by photoluminescence (PL), photoinduced absorption (PIA) and electron spin resonance (ESR). The donor materials used were P3HT and MEH‐PPV. As acceptors we employed PC₆₀BM as reference and various soluble C₇₀‐derivates: PC₇₀BM, two different diphenylmethano‐[70]fullerene oligoether (C₇₀‐DPM‐OE) and two dimers, C₇₀–C₇₀ and C₆₀–C₇₀. Blend films containing C₇₀ revealed characteristic spectroscopic signatures not seen with C₆₀. Light‐induced ESR showed signals at g ≥ 2.005, assigned to an electron localized on the C₇₀ cage. The formation of C₇₀ radical anions also leads to a subgap PIA band at 0.92 eV, hidden in the spectra of C₇₀‐based P3HT and MEH‐PPV blends, which allows for more exact studies of charge separated states in conjugated polymer:C₇₀ blends. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

EPR study on star-shaped copolymers containing C60 core

A series of novel star-shaped copolymers containing C₆₀ core [C₆₀(PPMS)_X(CH₃)_X, C₆₀(PMS)_X(CH₃)_X, C₆₀(PVK)_XH_X and C₆₀(PAN)_X(CH₃)_X] were prepared by reaction of C₆₀ with the livingn-butyl-terminated vinyl polymer which was synthesized via anionic polymerization reaction of a vinyl compound in the presence ofn-butyllithium. The results of the electron paramagnetic resonance (EPR) experiment indicated that the spectroscopic properties of the copolymers are different from their parent polymers and pure C₆₀. The star-shaped copolymers exhibited two kinds of paramagnetic species. The temperature dependence of the EPR spectra of the C₆₀(PAN)_X(CH₃)_X copolymer has also been investigated, and a pyrolytic mechanism of the formation of a new conjugated system for this copolymer is suggested.     

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.     

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.     

Thermal conductivity of C60 and C70 crystals

We have performed thermal conductivity measurements on C₆₀ and C₇₀ crystals grown by sublimation. For single crystal C₆₀, the thermal conductivity k is 0.4 W/m K at room temperature and is nearly temperature independent down to 260K. We observed a sharp orientational phase transition at 260K, indicated by a 25% jump in k. Below 90K, k is time dependent, which manifests itself as a shoulder-like structure at 85K. The temperature and time dependence of k below 260K can be described by a simple model which accounts for the thermally activated hopping of C₆₀ molecules between two nearly degenerate orientations, separated by an energy barrier of 240 meV. It is found that solvents have a strong influence on the physical properties of C₇₀ crystals. For solvent-free C₇₀ crystal, k is about constant above 300K. There is a broad first-order phase transition in k at 300K with a 25% jump. We associate this transition with the aligning of the fivefold axes of the C₇₀ molecules along the c-axis of the hexagonal lattice. Upon further cooling, k increases and is time independent.     

C60,C60/C70混合物在甲苯和1－甲基萘中的荧光光谱

测量了C60,C60/C70混合物分别在甲苯和1-甲基萘中的激发谱和荧光光谱,用532nm波长光为激发源。比较了纯C60及C60/C70混合物的荧光特性,对所观察到的发光谱进行了讨论。     

C_(60)、C_(70)的分子对称性与拉曼光谱

本文从C60、C70分子结构出发,通过群论计算得出他们的拉曼活性模式,并与实验观察到的光谱和相关文献中的预测相对比。对C60在金属基底上两种可能的吸附方式引起的分子对称性改变及相应的拉曼光谱作了分析,推测可能以六边形面方式吸附。     

Crystalline structure of a C60/C70 membrane

The crystalline structure of a C₆₀/C₇₀ membrane prepared by an original technique has been studied by x-ray diffraction and Raman spectroscopy. The effects of purification of the starting C₆₀/C₇₀ mixture to C₇₀ composition and of spatial separation of the C₆₀ and C₇₀ phases in the membrane have been revealed. The samples studied were established to have a composition gradient from C₆₀ to C₇₀. The main structure of the membrane is shown to be an fcc lattice with a=14.308 Å.     

Electron energy-loss spectroscopy studies on C60 and C70 fullerite

The electronic structure of the crystalline fullerites C₆₀ and C₇₀ has been investigated by high-energy electron energy-loss spectroscopy in transmission. From valence band excitations and from core-level excitations of the C 1s level information on occupied and unoccupied and bands has been obtained.     

Paramagnetic relaxation kinetics of the cation radical C 60 + in C60 powder

The kinetics of spin-lattice and phase relaxation of C ₆₀ ⁺ radicals in C₆₀ powder has been studied at room temperature by pulsed EPR. It is found that the kinetics can be described by the relation exp $( - a\sqrt t )$ characteristic of the case in which the paramagnetic centers are distributed over relaxation times. It is concluded that the observed kinetics are due to the presence of oxygen molecules, which act as a fast-relaxing impurity and accelerate the relaxation of the C ₆₀ ⁺ radicals. The results obtained offer an explanation for a number of features of C ₆₀ ⁺ relaxation in fullerites discovered earlier.