Complementary Multiple Hydrogen Bonding Interactions Induce the Self-Assembly of Supramolecular Structures from Heteronucleobase-Functionalized Benzoxazine and Polyhedral Oligomeric Silsesquioxane Nanoparticles

Abstract

We prepared octuply adenine (A)-functionalized polyhedral oligomeric silsesquioxane [(octakis(vinylbenzyladenine-siloxy)silsesquioxane, OBA-POSS] nanoparticles through the reaction of A with octakis(benzyl chloride) POSS (OVBC-POSS), itself prepared through hydrosilylation of octakis(dimethylsiloxy)silsesquioxane (Q8M8H) with vinyl benzyl chloride. We observed the self-assembly of lamellar structures from the complexation of a thymine (T)-functionalized polybenzoxazine (PA-T) with OBA-POSS, stabilized through complementary multiple hydrogen bonding interactions between the T groups of PA-T and the A groups of OBA-POSS. In addition, incorporating POSS presenting multiple, strong, complementary hydrogen bonding A units into the PA-T matrix significantly enhanced the thermal stability of this polymer, as evidenced using differential scanning calorimetry and thermogravimetric analysis.