Crystal structures of 3,3'-bis-(hy-droxy-dimethylsilan-yl)azo-benzene and 4,4'-bis-(hy-droxy-dimethyl-silane)azo-benzene.

The title compounds {systematic names (E)-[diazene-1,2-diylbis(3,1-phenyl-ene)]bis-(di-methyl-silanol) and (E)-[diazene-1,2-diylbis(4,1-phenyl-ene)]bis-(di-methyl-silanol)}, both of the sum formula C16H22N2O2Si2, were obtained by transmetallation of the respective bis-stannylated azo-benzenes with di-chloro-dimethyl-silane and esterification followed by hydrolysis. The asymmetric unit of 3,3'-diazenediylbis[dimeth-yl(phen-yl)silanol] (with the silanol functional group in a meta position) consists of two mol-ecules, of which one occupies a general position, whereas the second is located on a centre of inversion. In 4,4'-diazenediylbis[dimeth-yl(phen-yl)silanol] (with the silanol functional group in a para position) likewise two mol-ecules are present in the asymmetric unit, but in this case both occupy general positions. Differences between all mol-ecules can be found in the torsions about the N=N bond, as well as in the dihedral angles between the benzene rings. In both structures, inter-molecular O-H⋯O hydrogen bonding is observed, leading to the formation of layers parallel to (01-1) for (I) and to chains parallel to the a axis for (II).

Formation and Reversible Morphological Transition of Bicontinuous Nanospheres and Toroidal Micelles by the Self-Assembly of a Crystalline-b-Coil Diblock Copolymer.

We herein report the formation of two complex nanostructures, toroidal micelles and bicontinuous nanospheres, by the self-assembly of the single structurally simple crystalline-b-coil diblock copolymer poly[bis(trifluoroethoxy)phosphazene]-b-poly(styrene), PTFEP-b-PS, in one solvent (THF) and without additives. The nature of these nanostructures in solution was confirmed by DLS and cryo-TEM experiments. The two morphologies are related by means of a new type of reversible morphological evolution, bicontinuous-to-toroidal, triggered by changes in the polymer concentration. WAXS experiments showed that the degree of crystallinity of the PTFEP chains located at the core of the toroids was higher than that in the bicontinuous nanospheres, thus indicating that the final morphology of the aggregates is mostly determined by the ordering of the PTFEP core-forming blocks.

Polyphosphazenes for the Stille reaction: a new type of recyclable stannyl reagent.

A random phosphazene copolymer {[N = P((CH2)7-Br)Ph]0.5[N = PMePh]0.5}n (2) and a block copolyphosphazene {[N = P((CH2)7-Br)Ph]0.5[N = PMePh]0.5}45-b-[N = P(O2C12H8)]55 (5), having a branch with two randomly distributed units, have been synthesized and used as precursors for the stannyl derivatives {[N = P((CH2)7-SnBu2An)Ph]0.5[N = PMePh]0.5}n (3) and {[N = P((CH2)7-SnBu2An)Ph]0.5[N = PMePh]0.5}45-b-[N = P(O2C12H8)]55 (6, An = p-MeOC6H4). Polymers 3 and 6 were tested as recyclable tin reagents in the Stille cross-coupling reaction with ArI, using various Pd catalysts and different experimental conditions. Polymer 6 can be recycled without a significant release of tin, but its efficiency decreased after three consecutive cycles. This effect was explained by studying the self-assembly of the polymer under the same conditions used for the catalytic experiments, which evidenced the progressive coalescence of the polymeric vesicles (polymersomes) leading to stable and bigger core-shell aggregates by the attraction of the [N = P(O2C12H8)] rich membranes, thus decreasing the accessibility of the tin active centers.