Over the past two decades, organic optoelectronic materials have been considered very promising. The attractiveness of this group of compounds, regardless of their undisputable application potential, lies in the possibility of their use in the construction of organic–inorganic hybrid materials. This class of frameworks also considers nanostructural polyhedral oligomeric silsesquioxanes (POSSs) with “organic coronae” and precisely defined organic architectures between dispersed rigid silica cores. A significant number of papers on the design and development of POSS-based organic optoelectronic as well as photoluminescent (PL) materials have been published recently. In view of the scientific literature abounding with numerous examples of their application (i.e., as OLEDs), the aim of this review is to present efficient synthetic pathways leading to the formation of nanocomposite materials based on silsesquioxane systems that contain organic chromophores of complex nature. A summary of stoichiometric and predominantly catalytic methods for these silsesquioxane-based systems to be applied in the construction of photoactive materials or their precursors is given.

Polyhedral oligomeric silsesquioxanes (POSS) with a rigid inorganic Si-O-Si core and flexible and reactive and/or inert organic coronae have attracted much attention. Their unique structures, in addition to their physical properties, e.g. low dielectric constant or high thermal stability, are especially interesting. The well-defined organization of silsesquioxanes is important due to their possible use as precursors and components of versatile inorganic/organic hybrid materials. This paper presents a short overview of the two parallel paths in current research on double-decker silsesquioxanes (DDSQ), i.e. the synthesis and properties of both molecular and macromolecular compounds based on a DDSQ core. Over the last decade the number of publications concerning DDSQ based compounds has increased showing the growing interest in this field. Several reviews on different aspects of POSS have been prepared; however, because of the relatively “young age” of the double-decker silsesquioxane there has not been a review of the above topic.

Double-decker silsesquioxanes have gained a high reputation in many branches of chemistry and process development. In particular, catalytic processes that convert double-decker silsesquioxanes into important functional classes of fine chemicals are a central topic of contemporary organosilicon chemistry. Although the 9,19-di(hydro)octaphenyl double-decker silsesquioxane (DDSQ-2SiH) is known, we report its cis and trans structure and X-ray structure for the first time. The combination of DDSQ-2SiH in a known hydrosilylation reaction protocol with precise reaction time control (FT-IR in situ apparatus) allowed us to selectively assemble a series of previously unreported molecular double-decker silsesquioxanes with ethyl bridged π-conjugated arenes. These compounds were used as a molecular model to obtain their respective macromolecular hybrid analogues. The obtained compounds were characterized spectroscopically and their thermal parameters were also verified.