Platinum complexes bearing bulky N-heterocyclic carbene (NHC) ligands, i.e., [Pt(IPr*)(dvtms)] (where, IPr* = 1,3-bis{2,6-bis(diphenylmethyl)-4-methylphenyl}imidazol-2-ylidene) and [Pt(IPr*OMe)(dvtms)] (where, IPr*OMe = 1,3-bis{2,6-bis(diphenylmethyl)-4-methoxyphenyl}imidazol-2-ylidene, dvtms = divinyltetramethyldisiloxane) catalyse nearly quantitatively and highly or completely the selective hydrosilylation of terminal olefins as well as terminal or internal acetylenes.
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.
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 functionalized dialkenylsilsesquioxanes were obtained by efficient and highly stereoselective silylative coupling and cross-metathesis of divinylsubstituted double-decker silsesquioxanes (DDSQ-2SiVi) with substituted styrenes and other olefins. Both reactions proceed highly stereoselectively and lead to nearly quantitative formation of E isomers. The optimized reaction conditions for styrene were adopted for successful silylative coupling polycondensation of DDSQ-2SiVi with 1,4-divinylbenzene yielding stereoregular cooligomer containing double-decker (silsesquioxyl-silylene)-vinylene-phenylene units.
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