Nonaqueous, molecular precursor route to hybrid inorganic/organic zirconia-silica materials containing covalently linked organic bridges

New hybrid inorganic/organic materials possessing zirconium in the inorganic framework have been synthesized. Co-thermolyses in sealed reactors (toluene, AlCl3 catalyst, 155 degreesC) of Zr[OSi((OBu)-Bu-t)(3)](4) in the presence of (EtO)(3)Si(CH2)(n)Si(OEt)(3) (n = 1, 2) or (EtO)(3)Si(C6H4),Si(OEt)(3) (n = 1, 2; C6H4 = 1,4-phenylene) monomers rapidly yielded monolithic, transparent gels. The resulting xerogels were amorphous and exhibited high surface areas and high surface coverages of OH functionalities. Solid-state Si-29 and C-13 CP AUS NMR spectroscopies were used to establish the presence of intact, organic bridging groups and to verify the presence of unreacted ethoxy groups. Energy-dispersive X-ray spectroscopy was used to elucidate the elemental composition and distribution throughout the material, and atomic force microscopy was used to probe surface adhesive properties.