New directions in inorganic polymer and materials chemistry: Studies of metal germanium sulfides, ferrocene -containing materials, and mesoporous silica - poly(ferrocenylsilane) composites.

摘要

A novel condensation polymerization of [Ge4S10] 4- clusters in the presence of acid gave a high temperature, high-pressure polymorph of GeS2. Characterization by Rietveld refinement and Raman spectroscopy revealed that the structure contains [Ge4S 10] clusters intact and linked into two interpenetrating diamond-like lattices.;The first examples of mesostructured metal germanium sulfides were prepared and characterized. These materials display hexagonal symmetry akin to MCM-41. Moreover, the channel diameters may be modified by varying the surfactant employed in the preparation. A liquid crystal templating mechanism in formamide has been proposed as the source of the mesoscopic organization of the materials.;Investigations into the spirocyclic [1]silaferrocenophanes has expanded into several fields. Using these ferrocenophanes as precursors, a variety of new materials and molecular chemistry has been developed. Among these, we have discovered convenient routes to ferrocenylchlorosilanes, ferrocenylsilanols, ferrocenylsiloxanes, poly(ferrocenylsilane) thermosets and gels, and shaped magnetic ceramics.;[1]Silaferrocenophanes have been incorporated into the well-ordered channels of MCM-41 and subsequently pyrolyzed to yield a superparamagnetic mesostructured ceramic. An investigation of the magnetic properties of the material revealed that the ceramic contains superparamagnetic iron nanoparticles, which are capped with an iron silicate coating and confined to the channels of mesoporous silica.