Langmuir and Langmuir–Blodgett Films of Unsymmetrical and Fully Condensed Polyhedral Oligomeric Silsesquioxanes (POSS)

The search for novel building blocks for preparation of nanostructures of unique properties is crucial for development of functional nanomaterials. Polyhedral oligomeric silsesquioxanes (POSS) may be regarded as organic–inorganic nanoparticles of unusual characteristics, i.e., monodisperse size, high temperature resistance, and small dielectric constant. Here, we study four derivatives of fully condensed polyhedral oligomeric octasilsesquioxanes. Seven corners of the POSS cages are substituted with isobutyl groups forming a hydrophobic tail, whereas the eighth substituent acts as a hydrophilic head due to a judiciously chosen functional group. Such design assures amphiphilic character of POSS molecules with well-defined hydrophilic head and hydrophobic tail. The combination of amphiphilicity, well-defined size and composition, and rheological properties of monolayers makes studied POSS interesting model for self-assembly, thin films, and interfacial investigations. The Langmuir–Blodgett technique is used as a method that provides the best control over the parameters of thin films formation. The functional hydrophilic group strongly influences the behavior of POSS at the air/water interface. The mercapto derivative, which seems most promising for preparation of complex nanostructures, appears to form aggregates and multilayer films. Three other studied derivatives (bearing glycerol unit, maleamic acid, and amino group) behave as classical amphiphiles at the air/water interface.