625417-05-2Relevant articles and documents
Corner- and Side-Opened Cage Silsesquioxanes: Structural Effects on the Materials Properties
Imoto, Hiroaki,Ueda, Yukiho,Sato, Yuri,Nakamura, Masashi,Mitamura, Koji,Watase, Seiji,Naka, Kensuke
, p. 737 - 742 (2020)
Open-cage silsesquioxane, in which traditional closed-cage silsesquioxane is partially hydrolyzed, is a promising class of building blocks for constructing organic-inorganic hybrids. It has advantages of high thermal stability, low crystallinity, transparency, designability, etc. Although the structural effects of closed-cage silsesquioxanes have been elucidated in detail so far, those of open-cages have never been studied. Herein, we synthesized corner- and side-opened cage silsesquioxanes having carbazole units at the open moieties. The former was amorphous in the solid state and polymer matrix, while the latter formed crystalline structures. These different packing structures caused significant difference in the performance as an emission layer of organic light emitting device.
Synthesis of Functionalized Silsesquioxane Nanomaterials by Rhodium-Catalyzed Carbene Insertion into Si?H Bonds
Franz, Annaliese K.,Jagannathan, Jake R.,Targos, Karina
supporting information, (2021/11/27)
We report carbene insertion into Si?H bonds of polyhedral oligomeric silsesquioxanes (POSS) for the synthesis of highly functionalized siloxane nanomaterials. Dirhodium(II) carboxylates catalyze insertion of aryl-diazoacetates as carbene precursors to afford POSS structures containing both ester and aryl groups as orthogonal functional handles for further derivatization of POSS materials. Four diverse and structurally varied silsesquioxane core scaffolds with one, three, or eight Si?H bonds were evaluated with diazo reactants to produce a total of 20 new POSS compounds. Novel diazo compounds containing a fluorinated octyl group and boron-dipyrromethene (BODIPY) chromophore demonstrate the use of highly functionalized substrates. Transformations of aryl(ester)-functionalized POSS compounds derived from this method are demonstrated, including ester hydrolysis and Suzuki–Miyaura cross-coupling.
Highly Efficient Catalytic Route for the Synthesis of Functionalized Silsesquioxanes
Ka?mierczak, Joanna,Kuciński, Krzysztof,Hreczycho, Grzegorz
supporting information, p. 9337 - 9342 (2017/08/14)
Silsesquioxanes (POSS) have recently become the subject of growing interest in many branches of materials chemistry. Despite this great interest, no direct metal-catalyzed method to cap the corner of the POSS molecules has yet been proposed. In this report, we present a highly efficient method for the synthesis of functionalized silsesquioxanes mediated by scandium(III) triflate, which opens up the possibility of introducing a wide variety of functional groups into this class of organosilicon compounds under mild conditions with excellent yields. We also investigated the differences in the activity of the Lewis acid (Sc(OTf)3) and the hidden Br?nsted acid (TfOH) generated in situ from triflates as catalysts in the functionalization of silsesquioxanes. What is more, this solution provides an efficient corner-capping reaction and other functionalizations to obtain silsesquioxane derivatives which are often not possible to synthesize with good yields, efficiency, and chemoselectivity using conventional methods.
