Solid-State Polycondensation via Ionic-to-Covalent Bond Transformation to Control Polymer Structure: Preparation of Porphyrin-Based Ladder Polymer.

The controlled formation and the regular arrangement of polymer chains have been performed by novel solid-state polycondensation including the ionic-to-covalent bond transformation in the ionic molecular crystals. The combination of the tetra-anion and -cation of tetraphenylporphyrin derivatives, tetrakis(benzylpyridinium carboxylate), was found to form layered crystal structures and underwent thermal solid-state polycondensation, thus, releasing the pyridine and forming the benzyl ester linkages. Powder X-ray diffraction, when compared to the monomer crystal structure data, suggested that the ladder polymer was produced with a layered structure.

Rhodium(I)-catalyzed silylation of aryl halides with triethoxysilane: practical synthetic route to aryltriethoxysilanes.

[reaction: see text] The specific silylation of aryl iodides and bromides with triethoxysilane (EtO)(3)SiH in the presence of NEt(3) and a catalytic amount of [Rh(cod)(MeCN)(2)]BF(4) provides the corresponding aryltriethoxysilanes in high yield.