title: Synthesis and isolation of methacrylate- and acrylate-functionalized polyhedral oligomeric silsesquioxanes (T8, T10, and T12) and characterization of the relationship between their chemical structures and physical properties.
abstract: Novel organic-inorganic hybrid nanobuilding blocks of methacrylate- and acrylate-functionalized polyhedral oligomeric silsesquioxanes were easily prepared via nucleophilic substitution on octakis(3-chloropropyl)octasilsesquioxane, using sodium methacrylate and sodium acrylate, respectively. From a practical standpoint, these cage-rearranged silsesquioxanes (T8, T10, and T12) could be readily isolated in their pure form with conventional silica gel column chromatography. Octakis(3-propyl methacrylate)octasilsesquioxane (T8) is a colorless, crystalline solid with a melting point of 66.7-67.2 °C, while other cage products are colorless viscous liquids at room temperature. Moreover, we report that the chemical structure/physical property relationship of silsesquioxane cages not only is dependent on the symmetry of the inorganic silsesquioxane core at a given temperature but also is dictated by the organic substituent mobility. Structures of the products were confirmed by (1)H, (13)C, and (29)Si NMR spectroscopy and high resolution electrospray ionization mass spectrometry analysis.
authors.affiliation: Department of Chemistry, Center of Excellence for Innovation in Chemistry (PERCH-CIC), and ‡Capability Building Unit for Nanoscience and Nanotechnology, Faculty of Science, Mahidol University , Rama VI Road, Ratchathewi, Bangkok 10400, Thailand.
authors.forename: Vuthichai
authors.initials: V
authors.lastname: Ervithayasuporn
authors.forename: Supansa
authors.initials: S
authors.lastname: Chimjarn