A covalently-linked microporous organic-inorganic hybrid framework containing polyhedral oligomeric silsesquioxane moieties

Abstract

By a Yamamoto-type of Ullmann cross-coupling reaction, a well-defined covalently-linked microporous organic-inorganic hybrid framework polyoctaphenylsilsesquioxane (JUC-Z1) was effectively prepared from the nano building block p-iodio-octaphenylsilsesquioxane (I8OPS) with a yield of ca. 100%. The structure of JUC-Z1 was characterized by (13)C CP/MAS NMR and (29)Si MAS NMR experiments. Fourier transform infrared spectroscopy (FTIR) was performed to confirm the presence of functions in the framework. The results showed that inorganic silsesquioxane cubes were linearly covalently-linked by biphenyls, offering a highly cross-coupling framework. The powder X-ray diffraction (PXRD) pattern and transmission electron microscope (TEM) image show that JUC-Z1 is spherical with uniform micropores. N(2) adsorption results suggest that the hybrid framework has a narrow pore size distribution from 11.8 to 20.0 Å, with a BET surface area of 283 m(2)g(-1) and a pore volume of 0.226 cm(3)g(-1). A thermogravimetric (TG) analysis indicates the thermal stability of JUC-Z1 up to 397 °C in air. Moreover, a liquid sorption experiment reveals the favorable sorption of benzene and water.