Synthesis of a “Butterfly Cage” Based on a Double‐Decker Silsesquioxane

Abstract

Novel polyhedral structures were prepared with a butterfly‐shape composed of oligosiloxane wings and a double‐decker silsesquioxane (DDSQ) body. The compounds were synthesized in two steps from commercially available alkoxysilanes, and their structures were confirmed using spectroscopic methods and X‐ray crystallography. Not like other phenyl‐substituted cage silsesquioxanes, these butterfly cages show very good solubility in common organic solvents. The crystal structures clearly showed their unique features: a larger space with longer siloxane chains and a very flexible framework. Moreover, these compounds are thermally stable with a Td5 (5 % weight loss temperature) over 320 °C.

Vinyl-Functionalized Janus Ring Siloxane: Potential Precursors to Hybrid Functional Materials

“…The lone signal of the T unit Si in the 29 Si NMR spectrum of each product confirmed the conservation of the all-cis structure. All target Janus ring products are colorless viscous liquids with lower thermal properties (e.g., glass transition temperature or melting temperature) and lower crystallinity than previously reported tricyclic laddersiloxanes, double-decker, or octahedral oligomeric silsesquioxanes T 8 [25,26,[86][87][88][89][90][91].…”

Synthesis of Tricyclic Laddersiloxane with Various Ring Sizes (Bat Siloxane)

“…In the absence of water, the electrophilic silicon atom is attacked by the Lewis‐basic oxygen atom from another side chain ([T 4 ]–O–SiMe 2 H), affording a six‐membered side ring and Me 2 SiH 2 gas as a byproduct, as observed by Chojnowski and Rubinsztajn group. [ 34 ] Similarly to their report, the formation of 6‐membered ring with the hydride transfer to another SiH terminal functional groups lead to the formation of Me 2 SiH 2 gas. The release of Me 2 SiH 2 was confirmed by 29 Si NMR spectroscopy (Figure S33, Supporting Information).…”

“…The structures of all isolated products were confirmed using multinuclear NMR spectroscopy, matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry, and X-ray crystallography as shown in Supporting information. For structural verification of the products, crystalline samples were examined using X-ray crystallography and the results were compared with the reported structures [19,20,34,35] and shown in Table 2.…”

Synthesis and Characterization of Unsymmetrical Double-Decker Siloxane (Basket Cage)

“…Dichlorodisiloxane 1 [37] was freshly prepared by the hydrolytic condensation of dichlorodiphenylsilane in the presence of water for 3 h. The product obtained after distillation was a viscous colorless oil in 35% yield. The synthesis procedure for DDSQ-ONa ( 2 ) is described in detail in previous reports [19,21,38]. A 2-propanol solution of trimethoxyphenylsilane with NaOH and water was refluxed for 4 h, followed by continuous stirring at room temperature for 15 h. After filtration, a white solid was obtained in 58% yield.…”