Bis(μ6‐cis‐2,4,6,8,10,12,14,16‐octa­methyl­cyclo­octa­siloxane‐2,4,6,8,10,12,14,16‐octolato)octa­kis[(dimethyl­formamide)copper(II)] dimethyl­formamide solvate enclosing a pyrazine mol­ecule

The title compound, [Cu₈(C₈H₂₄O₂Si)₂(C₃H₇NO)₈]·C₄H₄N₂·C₃H₇NO, features a sandwich‐like cage enclosing a pyrazine mol­ecule, both situated on a centre of inversion. In addition, the crystal structure contains one dimethyl­formamide mol­ecule which is disordered over a centre of inversion. The copper layer, containing eight atoms, is located between two siloxanolate fragments. The whole structure of Cu atoms and siloxanolate rings is distorted by the pyrazine mol­ecule, leading to an oval form. As a result, the angles between the Cu atoms differ at the copper layer. The difference in the angles could lead to some deviations in the Cu–Cu exchange inter­actions within the copper ring, which is of inter­est for mol­ecular magnetism.     

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Dielectric relaxation analysis of starch oligomers and polymers with respect to their chain length

Starch belongs to the polyglucan group. This type of polysaccharide shows a broad β-relaxation process in dielectric spectra at low temperatures, which has its molecular origin in orientational motions of sugar rings via glucosidic linkages. This chain dynamic was investigated for α(1,4)-linked starch oligomers with well-defined chain lengths of 2, 3, 4, 6, and 7 anhydroglucose units (AGUs) and for α(1,4)-polyglucans with average degrees of polymerization of 5, 10, 56, 70, and so forth (up to 3000; calculated from the mean molecular weight). The activation energy (E_a) of the segmental chain motion was lowest for dimeric maltose (E_a = 49.4 ± 1.3 kJ/mol), and this was followed by passage through a maximum at a degree of polymerization of 6 (E_a = 60.8 ± 1.8 kJ/mol). Subsequently, E_a leveled off at a value of about 52 ± 1.5 kJ/mol for chains containing more than 100 repeating units. The results were compared with the values of cellulose-like oligomers and polymers bearing a β(1,4)-linkage. Interestingly, the shape of the E_a dependency on the chain length of the molecules was qualitatively the same for both systems, whereas quantitatively the starch-like substances generally showed higher E_a values. Additionally, and for comparison, three cyclodextrins were measured by dielectric relaxation spectroscopy. The ringlike molecules, with 6, 7, and 8 α(1,4)-linked AGUs, showed moderately different types of dielectric spectra. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 188–197, 2004     

Magnetic phases in Mn<Subscript>1</Subscript>_<Subscript>x</Subscript>Fe<Subscript>x</Subscript>WO<Subscript>4</Subscript> studied by neutron powder diffraction

The magnetic structures of Mn_1-xFe_xWO₄ with x = 0.0, 0.16, 0.21, 0.225, 0.232, 0.24, 0.27, 0.29, and 1.0 were refined from neutron powder diffraction data. The magnetic phase diagram could be completed in the coexistence range of different magnetic structures up to x = 0.29. For the magnetic state at 1.5 K a commensurate antiferromagnetic structure with a propagation vector = (±1/4, 1/2, 1/2) was found for x ⩽ 0.22 while the magnetic spins order with = (1/2, 0, 0) for x ≥ 0.22. In the latter phase, additionally, weak magnetic reflections indexed to an incommensurate ordering with = (- 0.214, 1/2, 0.457) occur in the diffraction pattern up to x = 0.29 indicating the occurence of a reentrant phase. For 0.12 ⩽ x ⩽ 0.29 the low temperature phases are separated from a magnetic high temperature phase showing only magnetic reflections indexed to a spin arrangement with = (1/2, 0, 0). The magnetic phase diagram is discussed qualitatively considering random superexchange between the statistically distributed Mn²⁺- and Fe²⁺-ions in the coexistence range 0.12 ⩽ x ⩽ 0.29 of different magnetic structures related to those of pure MnWO₄ and FeWO₄. Received 9 October 2002 Published online 14 March 2003     

Characterisation of adsorbed layers on sulphide minerals by photoelectron spectroscopy

The systems galena/2-mercaptobenzothiazole (MBT) and pyrite/MBT have been studied using synchrotron radiation excited photoelectron spectroscopy (SRXPS). The chemisorption of MBT and the multilayer formation of 2,2′-dithiobis(benzothiazole) (BBTD) are evidenced by additional structures, observed beside the substrate signals, in the S2p-spectra of cleaved mineral surfaces after adsorption of MBT. The amount of the complex remains constant at concentrations as high as 10^–5 mol/L whereas the amount of BBTD increases. From the dependence of the adsorbate intensities on the excitation energy the conclusion can be drawn that an overlayer of BBTD on a chemisorbed layer of MBT is formed. The very weak adsorption of MBT on pyrite in alkaline solutions may explain the selective flotation of galena from pyrite in alkaline media.