Herein, we report an efficient synthesis and functionalization of trifunctional open-cage-type silsesquioxanes. The method proposed has been successfully applied for the synthesis of a library of incompletely condensed silsesquioxanes with vinyldiorganosilyl functional groups, which allows further modification. Detailed studies of hydrosilylation of sterically different open-cage vinylsilsesquioxanes with a wide spectrum of phenylsilanes catalyzed by platinum and rhodium compounds are also reported. The influence of the reaction parameters, types of reagents, and catalysts employed on the efficiency of the process was examined. Optimization of the process based on the above results permitted the design of a very attractive method for the synthesis of multifunctionalized silsesquioxanes with excellent yields and regioselectivity. Moreover, the results allowed the choice of the most efficient catalyst whose application led to the selective formation of substituted open-cage silsesquioxanes. These new compounds have been fully characterized and studied in terms of their thermal properties.

An efficient synthesis and characterization of several new, conjugated styryl-carbazole compounds functionalized by monovinylsilanes in a stereocontrolled approach is presented. All N-organic derivatives were successfully examined in silylative coupling in the presence of ruthenium-hydride complexes 4 and 5. Furthermore, a novel class of vinylene–arylene linear oligomeric materials with 1,4-bis(dimethylvinylsilyl)naphthalene in the main chain was produced. Both reactions proceed very effectively, stereo- and regioselectively, allowing one to obtain E-isomer derivatives with high isolation yields.

A facile and efficient Pd-based Suzuki–Miyaura coupling reaction leading to mixed chromophores with styryl fragments, enabling their further application, is presented. We also disclose their use in the formation of monofunctionalized silsesquioxanes with a chromophore group covalently bound to a T₈ core that have been prepared via a cross-metathesis reaction. These new materials were studied in terms of their photophysical and also thermal properties.