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, AlCl 3 catalyst, 155 °C) of Zr[OSi(O t Bu) 3 ] 4 in the presence of (EtO) 3 Si(CH 2 ) n Si(OEt) 3 ( n = 1, 2) or (EtO) 3 Si(C 6 H 4 ) n Si(OEt) 3 ( n = 1, 2; C 6 H 4 = 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 29 Si and 13 C CP MAS 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.