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Infrared spectra of La2@C80 and a series of Ce-based endohedral metallofullerenes (EMFs), including Ce@C82, Ce2@C72, Ce2@C78, and Ce2@C80 are reported. DFT calculations are used for their thorough analysis and assignment. The vibrations of the fullerene cages in all studied EMFs differ from those of their empty, charged cage analogues. Furthermore, EMFs with the same carbon cage but different type of encapsulated species also show significant differences in their cage vibrational patterns. These phenomena are explained by a different coupling of the vibrational modes as well as by the different charge distributions in EMFs and empty, isostructural fullerene anions.

A recently developed rotating spectroelectrochemical cell for in situ Raman spectroscopic studies of photoreactive compounds without marked decomposition of the sample is presented. Photochemically unstable compounds like fullerenes are difficult to be studied under stationary conditions by in situ spectroelectrochemistry using laser excitation as in Raman spectroscopy. Therefore, a rotating spectroelectrochemical was developed to avoid these difficulties. The cell can be used for any type of a planar electrode and of electrode materials in contact with aqueous or non-aqueous solutions as well as ionic liquids under appropriate laser power and accumulation times. The innovative advantage consists in the precession movement of the spectroelectrochemical cell with an eccentric drive. This precession movement allows a fixed electrical connection to be applied for interfacing the electrochemical cell to a potentiostat. Hence, any electrical imperfections and noise, which would be produced by sliding contacts, are removed. Further advantage of the rotating cell is a dramatic decrease of the thermal load of the electrochemical system. The size of the spectroelectrochemical cell is variable and dependent on the thickness of the cuvettes used ranging up to ca. 10 mm. The larger measuring area causes a higher sensitivity in the spectroscopic studies using this cell. The as constructed spectroelectrochemical cell is easy to be handled. The application of the cell is demonstrated for ordered fullerene C60 layers and the spectroelectrochemical behavior of nanostructured fullerenes. Here the charge transfer at highly ordered fullerene C60 films was studied by in situ Raman spectroelectrochemistry under appropriate laser power and accumulation time without marked photodecomposition of the sample.

International audience; We report a study of the electronic structure and charge transfer in the metallofullerene Sc 3 N@C 80 using photoemission and x-ray absorption spectroscopy. Through a comparison of the x-ray absorption spectrum of Sc 3 N@C 80 at the Sc L 2,3 edge with atomic multiplet calculations, the Sc 3d electron count is determined to be 0.6, thus giving an effective Sc valency of 2.4. With the N atom gaining a full electronic shell by means of covalent bonding with the Sc ͑also involving the Sc 3d electron density observed in the x-ray absorption experiments͒, the remaining six valence electrons of the Sc 3 N cluster are then transferred to the carbon cage which stabilizes the C 80 cage structure with I h symmetry, a structure which is not energetically favored in neutral C 80. The presence of the highly symmetric I h cage structure is further supported by the observation of distinct fine structure in the valence band photoemission spectra of the endohedral, which results from the high degree of effective degeneracy of the electronic states in the molecule. Finally, the results of investigations of K-doped Sc 3 N@C 80 using photoemission give insight into the K x Sc 3 N@C 80 phases that are formed upon intercalation.

Poly (dithienothiophene)s (PDTTs), low band-gap conjugated polymers with poly thiophene-like chain where an aromatic thienothiophene moiety is fused to each thiophene ring, were studied using Raman spectroscopy, photoinduced infrared absorption, as well as attenuated total reflection Fourier transform infrared (ATR-FTIR) and electron spin resonance (ESR) spectroelectrochemistry. The spectroelectrochemical studies were performed in situ during p- and n-doping (electrochemical oxidation and reduction, respectively). Raman lines of the pristine polymers are compared to infrared active vibration (IRAV) bands due to the charge carriers injected by the electrochemical doping processes or by illumination. The different pi-electron distribution along the polythiophene-like chain, which determines the different band-gap sizes, also account for the different lattice relaxations and vibrational behaviors shown by these polymers. By means of in situ ESR spectroscopy, the formation of paramagnetic positive and negative charge carriers with unusually high g-factors could be proved.

Poly(dithienothiophene)s (PDTTs), low band-gap conjugated polymers with polythiophene-like chain where an aromatic thienothiophene moiety is fused to each thiophene ring, were studied using Raman spectroscopy, photoinduced infrared absorption, as well as attenuated total reflection Fourier transform infrared (ATRFTIR) and electron spin resonance (ESR) spectroelectrochemistry. The spectroelectrochemical studies were performed in situ during p- and n-doping (electrochemical oxidation and reduction, respectively). Raman lines of the pristine polymers are compared to infrared active vibration (IRAV) bands due to the charge carriers injected by the electrochemical doping processes or by illumination. The different ð-electron distribution along the polythiophene-like chain, which determines the different band-gap sizes, also account for the different lattice relaxations and vibrational behaviors shown by these polymers. By means of in situ ESR spectroscopy,the formation of paramagnetic positive and negative charge carriers with unusually high g-factors could be proved

[60]Fullerene is oxidized to its radical cation at preparative scale by means of photoinduced electron transfer (PET). In general, C-60(.+) reacts with various H-donors such as alcohols, aldehydes, ethers etc., under formation of 1,2-dihydro[60]fullerenes. In case of tert-butanol, propionic acid and glycol, for example, product formation is also initiated by H-abstraction from the OH group. Both time-resolved laser flash photolysis studies and ESR spectroscopic investigations clearly demonstrate the formation of C-60(.+) using PET conditions. Upon addition of H-donors such as methanol the signal of C-60(.+) is quenched as monitored both by laser flash photolysis and ESR spectroscopy. Based on these studies we assume the oxidation of C-60 followed by abstraction of hydrogen from the H-donor.