Cover Picture

The cover picture shows a section of the electron charge density of the first metal carbide endohedral metallofullerene (Sc(2)C(2))@C(84) obtained from a synchrotron X-ray powder diffraction study by the maximum entropy method (MEM). The several density maxima, which correspond to scandium and carbon atoms, are clearly seen inside the C(84) carbon cage. The MEM charge density distribution also reveals that the C(84) cage has D(2d) symmetry (no. 23) and that the C(2) axis is parallel to the <100> face-centered cubic (fcc) direction of the unit cell. As a consequence of the site symmetry being 4mm, the C(2) axis of (Sc(2)C(2))@C(84) is oriented to six equivalent <100> directions and shows a merohedral disorder. The resultant Sc small middle dot small middle dot small middle dotSc distances and C-C bond lengths of the Sc(2)C(2) cluster are 0.429(2) and 0.142(6) nm, respectively. The observed C-C bond length is between that of a typical single and a double bond, and is very close to that of the C-C bond (0.143 nm) combining two pentagons in a C(60) molecule. More about this fascinating structure can be found in the contribution by Shinohara and co-workers on p. 397 ff.     

Sequence distributions of vinyl chloride-vinyl acetate and vinyl chloride-vinyl propionate copolymers

¹³C-NMR spectroscopy was used in a detailed study of vinyl chloride-vinyl acetate and vinyl chloride-vinyl propionate copolymers. The NMR spectra of the methylene carbon region showed three split peaks whose intensities changed with composition of the copolymers. These peaks were assigned to diad sequences and the observed diad concentrations were in good agreement with the calculated concentrations in terms of the random copolymerization theory. For the methine carbon spectra of vinyl acetate or vinyl propionate units in the copolymers the degree of splitting of the signal was improved by the addition of tris(1,1,1,2,2,3,3-heptafluro-7,7-diemthyl-1,4,6-octanedinata)-praseodymium as a shift reagent. Four peaks assigned to the methine carbon were interpreted in terms of triad sequence distribution and tacticity.     

Angle-resolved photoemission study of the MX-chain compound [Ni(chxn)(2)Br]Br(2): spin-charge separation in hybridized d-p chains

We report on the results of angle-resolved photoemission experiments on a quasi-one-dimensional (1D) MX-chain compound [Ni(chxn)2Br]Br2, which shows a gigantic nonlinear optical effect. A "band" having about 500 meV energy dispersion is found in the first half of the Brillouin zone, but disappears at kb/pi approximately 1/2. These spectral features are well reproduced by the d-p chain model with a small charge-transfer energy Delta compared with that of 1D Cu-O compounds. We propose that this smaller Delta is the origin of the absence of clear spin-charge separation in the photoemission spectra and the strong nonlinear optical effect.     

Synthesis of antisense oligodeoxyribonucleotide analogues by use of deoxyribonucleoside 3′-bis(1, 1, 1, 3,3,3-hexafluoro-2-propyl) phosphites as new key intermediates

The deoxyribonucleoside 3′-bis(1,1,1,3,3,3-hexafluoro-2-propyl) phosphite units ( 3 ) are used in the chemical synthesis of oligodeoxyribonucleotides on solid supports. The new phosphite units ( 3 ) were prepared easily by reaction of nucleosides and tris-(1,1,1,3,3,3-hexafluoro-2-propyl) phosphite ( 2 ). They are readily activated by N-methylimidazole under very mild conditions on a solid support. This operation involves a one step reaction, which is an advantage over both the phosphite and H-phosphonate approaches. The use of deoxyribonucleoside phosphite intermediates in the synthesis of antisense oligodeoxyribonucleotides is also described.     

Quantitative estimation of trans-1,4 and cis-1,4 isomers in polychloroprene by high-resolution NMR

In the ¹H-NMR spectrum of polychloroprene dissolved in C₆D₆, the ?CH proton signal was separated into two triplet peaks. These triplet signals were assigned to the ?CH proton in the trans-1,4 and cis-1,4 isomers by measurement of ¹H-NMR spectra of 3-chloro-1-butene and a mixture of trans- and cis-2-chloro-2-butene as model compounds for the 1,2, trans-1,4 and cis-1,4 isomers. In ¹H-NMR spectra (220 Mcps) of polychloroprene dissolved in C₆D₆, two triplet signals were separated completely from which the relative concentrations of trans-1,4 and cis-1,4 isomers could be obtained quantitatively.     

Ionization condition of lithium ionic liquid electrolytes under the solvation effect of liquid and solid solvents

Ionization condition and ionic structures of the lithium ionic liquid electrolytes, LiTFSI/EMI-TFSI/(PEG or silica), were investigated through the measurements of ionic conductivity and diffusion coefficient. The size of the hydrodynamic lithium species (rLi) evaluated from the Stokes-Einstein equation was 0.90 nm before gelation with the PEG or silica. This reveals that the TFSI- anions from the solvent are coordinated on Li+ for solvation, forming, for example, Li(TFSI)4(3-) and Li(TFSI)2- in the electrolyte solution. By the dispersion of PEG for gelation, rLi increased up to 1.8 nm with the 10 wt % of PEG. This indicates that the lithium species is directly interacted with the oxygen sites on the polymer chains and the lithium species migrate, reflecting the polymer by hopping from site to site. In case of the silica dispersion, rLi decreased to 0.7 nm at 10 wt % silica. Although the silica surface with silanol groups fundamentally attracts Li+, the lithium does not migrate from site to site on the silica surface as in the gel of the polymer and follows random walk behavior in the network of the liquid-phase pathways in the two-phase gel. In the process, that solvated TFSI- anions are partially removed may be due to the attractive effect of H+, which was dissociated from the silanol group. It is concluded that the dispersed silica is effective to modify the hydrodynamic lithium species to be appropriate for charge transport as reducing the size and anionic charge of Li(TFSI)4(3-) by removing one or two TFSI- anions.