Highly Efficient Route for the Synthesis of a Novel Generation of Tetraorganofunctional Double‐decker Type of Silsesquioxanes

Abstract

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.

Polysiloxanes Grafted with Mono(alkenyl)Silsesquioxanes—Particular Concept for Their Connection

“…Preliminary tests were performed to optimize the reaction conditions in terms of the catalyst type and its amount. The Pt-based catalytic systems, i.e., (Pt 2 (dvds) 3 ), PtO 2 and (Pt(IPr*)(dvds)) (IPr* = 1,3-bis{2,6-bis(diphenylmethyl)-4-methylphenyl}-imidazol-2-ylidene) were selected due to their confirmed activity in the hydrosilylation reaction [52,[103][104][105][106][107]. The selection of toluene was based on the good solubility of all 1-5-RT 8 SQs as well as PS1-2.…”

Synthetic Routes to Silsesquioxane-Based Systems as Photoactive Materials and Their Precursors

“…The photophysical and thermal features could enable the application of these compounds in OLEDs devices. Our group studied the hydrosilylation of olefins and alkynes with silsesquioxanes with one, four and eight reactive Si–H moieties, which constitute a valuable group of precursors used in the formation of photoactive materials [93,94,95,96,97].…”

Double-Decker Silsesquioxanes Self-Assembled in One-Dimensional Coordination Polymeric Nanofibers with Emission Properties

“…All these features are of interest for multiple applications. , To date, scientific interest in silsesquioxanes was fixed mostly on functionalized cubic T 8 (mono- and octasubstituted) derivatives. ,− However, since the discovery of a new class of the so-called double-decker (DDSQ) type of silsesquioxane by Yoshida et al, it has attracted attention in the world of organosilicon compounds. − Studies on the synthesis of double-decker silsesquioxanes involve utility of the “closed” core derivatives, described as D 2 T 8 and the “open” core, i.e., M 4 T 8 , and refer to di- and tetrafunctionalized DDSQ compounds, respectively. This in turn affects the application of these systems in the formation of molecular and macromolecular DDSQ-based systems. − However, there have been a limited number of scientific reports concerning double-decker silsesquioxanes in comparison with cubic T 8 structures. This bottom-up approach toward formation of desired silsesquioxane derivatives has gained wide interest.…”