Thiolated Janus Silsesquioxane Tetrapod: New Precursors for Functional Materials

Herein, we report synthetic strategies for the development of a bifunctional Janus T₄ tetrapod (Janus ring), in which the orthogonal silsesquioxane and organic faces are independently functionalized. An all-cis T₄ 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 ²⁹Si, ¹³C and ¹H NMR, FTIR and TOF-ESI mass spectroscopy. To the best of our knowledge, this is one of the few reports of Janus T₄ tetrapods, with different functional groups located on both faces of the molecule, thus expanding the potential range of applications for these versatile precursors.