Hydrogen Bond-Mediated Self-Assembly of Polyhedral Oligomeric Silsesquioxane-Based Supramolecules

In this study, a functionalized pentaerythritol star polyester compound [tetrakis(nicotinoxymethyl)methane, TNMM] and an octakis[dimethyl(4-hydroxyphenethyl)siloxy]silsesquioxane (OP-POSS) were synthesized and used as tetrahedral and cubic building blocks, respectively, for three-dimensional, hydrogen-bond-mediated, polyhedral oligomeric silsesquioxane- (POSS-) based supramolecular network structures. With noncovalent chain extension of hydrogen bonds between its pyridine and phenol groups, the PUSS-based supramolecular networks exhibited thermally reversible properties. Compared with the glass transition temperature of OP-POSS (ca. 20 degrees C) and the melting temperature of TNMM (ca. 70 degrees C), the hydrogen-bond-mediated miscible blend of 40 wt % TNMM in OP-POSS exhibited a single and higher glass transition temperature (37 degrees C). Because of its strong intermolecular hydrogen bonding, the dewetting pattern of the blend of 40 wt % TNMM in OP-POSS formed ringlike structures rather than the droplets formed by pure OP-POSS. A transparent, brittle, and glassy solid at room temperature, the blend of 40 wt % TNMM in OP-POSS is an explicit and successful example of a PUSS-based hydrogen-bonded supramolecular network.