Fabrication of highly ordered Cu2+/Fe3+ decorated polyhedral oligomeric silsesquioxane hybrids: How metal coordination influences structure

Incorporation of isolated metal centers into well-organized nanostructures is a promising route in the development of the next generation of chemical, magnetic and electronic devices. In this work, a layer-by-layer protocol to grow highly ordered thin films of metal-decorated organic-inorganic cage-like polyhedral oligomeric silsesquioxane (POSS) is introduced. The key strategy is to use metal ions (Cu²⁺ or Fe³⁺) as linker for the amino-functionalized cage-like POSS, which are self-assembled between arachidic acid layers during Langmuir–Schaefer deposition. The Langmuir–Schaefer films are examined by X-ray photoelectron spectroscopy, X-ray diffraction, grazing incidence wide-angle X-ray scattering and extended X-ray absorption fine structure in order to understand how the coordination of metal ions influences the structure in the course of the layer-by-layer formation of the films.