The ability to self-assemble nanosized ligand-stabilized metal oxide or semiconductor materials offers an intriguing route to engineer nanomaterials with new tailored properties from the disparate components. We describe a novel one-pot two-step organometallic approach to prepare ZnO nanocrystals (NCs) coated with deprotonated 4-(dodecyloxy)benzoic acid (i.e., an X-type liquid-crystalline ligand) as a model LC system (termed ZnO-LC1 NCs). Langmuir and Langmuir-Blodgett films of the resulting hybrids are investigated. The observed behavior of the ZnO NCs at the air/water interface is rationalized by invoking a ZnO-interdigitation process mediated by the anchored liquid-crystalline shell. The ordered superstructures form according to mechanism based on a ZnO-interdigitation process mediated by liquid crystals (termed ZIP-LC). The external and directed force applied upon compression at the air/water interface and the packing of the ligands that stabilize the ZnO cores drives the formation of nanorods of ordered internal structure. To study the process in detail, we follow a nontraditional protocol of thin-film investigation. We collect the films from the air/water interface in powder form (ZnO-LC1 LB), resuspend the powder in organic solvents and utilize otherwise unavailable experimental techniques. The structural and physical properties of the resulting superlattices were studied by using electron microscopy, atomic force microscopy, X-ray studies, dynamic light scattering, thermogravimetric analysis, UV/Vis absorption, and photoluminescence spectroscopy.

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.