Thiolated Janus Silsesquioxane Tetrapod: New Precursors for Functional Materials

Herein, we report synthetic strategies for the development of a bifunctional Janus T(4) tetrapod (Janus ring), in which the orthogonal silsesquioxane and organic faces are independently functionalized. An all-cis T(4) tetrasilanolate was functionalized to introduce thiol moieties on the silsesquioxane face and naphthyl groups on the organic face to introduce luminescent and self-organization properties. The stepwise synthesis conditions required to prepare such perfectly defined oligomers via a suite of well-defined intermediates and to avoid polymerization or reactions over all eight positions of the tetrapod are explored via (29)Si, (13)C and (1)H NMR, FTIR and TOF-ESI mass spectroscopy. To the best of our knowledge, this is one of the few reports of Janus T(4) tetrapods, with different functional groups located on both faces of the molecule, thus expanding the potential range of applications for these versatile precursors.