We present an efficient methodology for the synthesis of tetrafunctionalized double-decker silsesquioxanes via hydrosilylation reaction. An investigation of the catalytic system, olefin structure, chemical and steric surrounding of SiÀ H moiety in the respective reagent was carried out on the progress, selectivity and rate of hydrosilylation process. Two alternative synthetic pathways for obtaining a variety of functionalized double-decker silsesquioxanes with high yields based on the Pt catalysts were developed. These parallel routes concern reverse SiÀ H and À CH=CH 2 reactive groups placement in the doubledecker silsesquioxane core. As a result, a series of new tetrasubstituted double-decker silsesquioxanes derivatives were obtained with high yield and selectivity and comprehensively characterized in detail by spectroscopic analyses.[a] J.

A series of double-decker silsesquioxane derivatives with four reactive functional groups were designed, efficiently synthesized, and characterized. These novel inorganic-organic hybrids show highly attractive features for applications as building blocks with Si-O-Si rigid cores (good thermal properties) with four reactive moieties, which can be functionalized in further processes.

This paper outlines an unexpected type of intramolecular transformation of DDSQ during hydrolytic condensation and surprising catalytic reactivity in silylative coupling.

The efficient one-pot procedure based on a sequence of hydrosilylation and reduction reactions was applied to obtain carbosilane dendrimers with different silsesquioxane (SQ) cores, i.e. from mono-T8SQ, octa-T8SQ to di- and tetrafunctional double-decker silsesquioxanes.

The urgent needs for photoactive materials in industry drive fast evolution of synthetic procedures in many branches of chemistry, including the chemistry of silsesquioxanes. Here, we disclose an effective protocol for the synthesis of novel double-decker silsesquioxanes decorated with two (styrylethynylphenyl)terpyridine moieties ( DDSQ_Ta-b ). The synthesis strategy involves a series of silylative and Sonogashira coupling reactions and is reported for the first time. DDSQ_Ta-b were employed as nanocage ligands to promote self-assembly in the presence of transition metals (TM), i.e., Zn 2+ , Fe 2+ , and Eu 3+ ions, to form one-dimensional (1D) coordination polymeric nanofibers. Additionally, ultraviolet-promoted and reversible E – Z isomerization of the C=C bond within the ligand structures may be exploited to tune their emission properties. These findings render such complexes promising candidates for applications in materials chemistry. This is the first example of 1D coordination polymers bearing DDSQ-based nodes with TM ions.

Silsesquioxanes containing Si‐OH functional groups are employed in many fields of chemistry as building blocks and reagents, but synthetic procedures for their synthesis may not always be so easy (due to parallel, possible side reactions) and, amongst other issues, generate significant amounts of chlorine waste. In this paper, we demonstrate an efficient, versatile and chlorine‐free synthetic procedure to obtain these systems. Reusable and highly active carbon‐supported palladium catalysts, as well as a commercially available Karstedt's catalyst were found to be active in the transformation of Si‐H anchored to various silsesquioxanes into corresponding Si‐OH and Si‐OR (R = alkyl, aryl) derivatives using water, alcohols, and phenols, respectively. A series of silsesquioxane compounds with the abovementioned functionalities was obtained and fully characterized.

A distinct look at known, hydrosilylation reactions used for the formation of DDSQ-based linear A–B alternating macromolecular systems with DPn > 1000 is presented. Selected physicochemical properties of obtained hybrid co-polymers were determined.

In the view of the fact that catalytic routes to design functionalized silsesquioxanes are currently of high importance, herein we report the effective functionalization procedure to obtain mono-, di-, and tetrasilylalkynylsubstituted silsesquioxanes of cubic T 8 and DDSQ type. The synthetic methodology is based on Ru-hydride complex that turned out to be an efficient catalyst for silylative coupling of ethynylsiloxysubstituted silsesquioxanes with vinylsilanes resulted in their silylalkynyl analogues. The ethynylsiloxysubstituted double-decker silsesquioxanes have been noted to be reactive in this process for the first time. A series of novel compounds were obtained, isolated, and characterized. Due to the presence of silylalkynyl moieties, they constitute an interesting family of Si−O−Si-based unique structures with potential applications.