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Abstract: Anion recognition by 1,3-disiloxane-1,1,3,3-tetraols has been elucidated by 1H NMR titrations and ESI-MS in organic solvents. The association constants of the receptors for halide anions are larger than those of silanediol and 1,3-disiloxane-1,3-diol due to the cooperative hydrogen bonds by four silanol hydroxy groups of 1,3-disiloxane-1,1,3,3-tetraols. [Copyright &y& Elsevier]

Abstract: 1H NMR dilution experiment and FTIR were used to investigate the hydrogen bonded interaction in three different types of incompletely condensed silsesquioxanes (POSS-mono-ol, POSS-diol and POSS-triol). For POSS-triol, there existed a dynamic equilibrium between single molecule and hydrogen-bonded dimer, and the dimerization constants (K dim) of POSS-triol in different solvents were determined by 1H NMR dilution experiment. In addition, based on hydroxy group which acted as hydrogen bond donors, the possibility of three POSS silanols as anion receptors to form host–guest complexes was also explored in this paper. [Copyright &y& Elsevier]

Abstract: To explore the anion recognition ability of silanol derivatives, ESI-MS and 1H NMR titrations of a 1,3-disiloxanediol 1 with anions were studied in CDCl3 and MeCN-d 3. The results indicate that 1 showed strong binding to anions such as AcO− and halides. [Copyright &y& Elsevier]

Hexaarylcyclotrisiloxane, which is one of the most stable derivatives of diarylsilanediol, was found to undergo palladium-catalyzed cross-coupling reaction with aryl halides in good yields. The reaction is performed in an aqueous medium taking potassium hydroxide as an activator. Both of the two aryl groups attached to each silicon atom could be utilized. Some base-sensitive functionality such as acetyl and nitro groups survived the reaction. [ABSTRACT FROM AUTHOR]

A vinyl-functionalized all-cis-tetrasiloxycyclotetrasiloxane [ViSi(OSiMe2H)O]4 (Vi = vinyl group) Janus precursor was prepared from potassium cyclotetrasiloxane silanolate. The Janus precursor was selectively modified at its dimethylhydrosilyl groups [–SiMe2H] via the Piers–Rubinsztajn reaction to obtain a family of new tetravinyl-substituted Janus rings [ViSi(OR')O]4 containing various functional groups in moderate yields. Remarkably, the tetravinyl groups on the structure remained intact after modification by the Piers–Rubinsztajn reaction. Since these synthesized compounds possess multiple functional groups (up to eight per molecule), they are potential precursors for advanced hybrid organic-inorganic functional materials. [ABSTRACT FROM AUTHOR]

The obtained novel, 12-8-12-membered ring laddersiloxane has a rigid silsesquioxane body with flexible oligosiloxane "wings". B Front Cover b : New bat siloxanes fly to the moon: Tricyclic laddersiloxanes with larger side rings are prepared for the first time from Janus rings. [Extracted from the article]

Dye-sensitized solar cells fabricated by using a novel metal-free alkoxysilyl carbazole as a sensitizing dye and a Co3+/2+-complex redox electrolyte exhibited light-to-electric energy conversion efficiencies of over 12% with open-circuit photovoltages higher than 1 V by applying a hierarchical multi-capping treatment to the photoanode. [ABSTRACT FROM AUTHOR]

A design of atomic and oligomer level structure in organic-inorganic hybrid materials is highly important for various applications. Nonaqueous acid-base reaction allows us to prepare silicophosphates with controlled inorganic networks (–(O–P–O–Si)n) at atomic level because phosphorous and silicon-based precursors can react directly, resulting in an alternating copolymer network. Organic functionalization in those materials has been realized so far by using organic-modified phosphorous acid and/or organo-chlorosilane as precursors. In the present study, silicophosphate oligomers exhibiting inorganic-organic hybrid chains of (–(O–P–O–Si–R–Si)n) (R: bridging organic functional groups), are prepared from phosphoric acid and organo-bridged bis(chlorosilane). The 1, 2-bis(chlorodimethylsilyl)ethane ((C2H4)(Me2SiCl)2) and 1, 4-bis(chlorodimethylsilyl)benzene ((C6H4)(Me2SiCl)2) were used as organo-bridged bis(chlorosilane). Different types of silicophosphate oligomers with different network structures and terminal groups (P-OH and/or Si-Cl) were prepared by changing the reaction temperature and molar ratio of precursors. The formation of low molecular weight oligomers of ring and cage morphologies (ring tetramer, cage pentamer, and ring hexamer) is suggested in the product prepared from phosphoric acid and (C6H4)(Me2SiCl)2 molecule at 150 °C. Those silicophosphate hybrid oligomers are expected to be used as building blocks of hybrid materials with well-defined network structures for desired functionalities. [ABSTRACT FROM AUTHOR]

Porous organosilica monoliths have attracted much attention from both the academic and industrial fields due to their porous structure; excellent mechanical property and easily functionalized surface. A new mercapto-functionalized silicone monolith from a precursor mixture containing methyltrimethoxysilane; 3-mercaptopropyltrimethoxysilane; and 3-mercaptopropyl(dimethoxy)methylsilane prepared via a two-step acid/base hydrolysis–polycondensation process was reported. Silane precursor ratios and surfactant type were varied to control the networks of porous monolithic gels. Gold nanoparticles were loaded onto the surface of the porous organosilica monolith (POM). Versatile characterization techniques were utilized to investigate the properties of the synthesized materials with and without gold nanoparticles. Scanning electron microscopy was used to investigate the morphology of the as-synthesized porous monolith materials. Fourier transform infrared spectroscopy was applied to confirm the surface chemistry. 29Si nuclear magnetic resonance was used to investigate the hydrolysis and polycondensation of organosilane precursors. Transmission electron microscopy was carried out to prove the existence of well-dispersed gold nanoparticles on the porous materials. Ultraviolet–visible spectroscopy was utilized to evaluate the high catalytic performance of the as-synthesized Au/POM particles [ABSTRACT FROM AUTHOR]

The hydrolysis–condensation reactions of m-tolyl, m-chlorophenyl, and α-naphtyl-trichlorsilanes, (1, 2, and 3, respectively) in water-acetone solutions were examined for how they were influenced by the change in the concentration of HCl (CHCl). The composition of the products was monitored by 29Si NMR spectroscopy and atmospheric pressure chemical ionization mass spectrometry (APCI-MS). The acidity of the medium was shown to affect the yields of the products, and so, what products were formed. For 3, e.g., APCI-MS showed peaks of α-naphtyl-T8 and α-naphtyl-T10 as the most abundant in the spectra taken after 48 and 240 h for the reaction conducted at CHCl = 0.037 mol L−1. Unlike this, at CHCl = 0.15 mol L−1, those peaks were of [α-naphtyl(HO)2SiO]2(α-naphtyl)(HO)Si and/or [α-naphtyl(HO)Si]3, [α-naphtyl(HO)Si]4,5, and α-naphtyl-T8 after 192 h. However, at both CHCl values, the main product (and an intermediate) after 24 h was trans-1,1,3,3-tetrahydroxy-1,3-di-α-naphtyldisiloxane. It was isolated and its structure established by 1H-, 29Si-NMR, and X-ray powder diffraction. [ABSTRACT FROM AUTHOR]

Low molecular weight, highly crosslinked silicone resins are widely used as reinforcing agents for highly transparent elastomers and adhesion/tack promoters in gels. The resins are complex mixtures and their structure / property relationships are ill defined. We report the synthesis of a library of 2, 3 and 4-fold hyperbranched polymeric oils that are comprised of linear, lightly branched or highly branched dendronic structures. Rheological examination of the fluids and tack measurements of gels filled with 10, 25 or 50% dendronic oils were made. Viscosity of the hyperbranched oils themselves was related to molecular weight, but more significantly to branch density. The properties are driven by chain entanglement. When cured into a silicone gel, less densely branched materials were more effective in improving tack than either linear oils or Me3SiO-rich, very highly branched oils of comparable molecular weight, because the latter oils underwent phase separation. [ABSTRACT FROM AUTHOR]

Our recent study on formal halide adducts of disilenes led to the investigation of the synthesis and properties of β-fluoro- and chlorodisilanides. The reaction of the functionalized neopentasilanes (Me3Si)3SiSiPh2NEt2 and (Me3Si)3SiSiMe2OMe with KOtBu in the presence of 18-crown-6 provided access to structurally related β-alkoxy- and amino-substituted disilanides. The obtained Et2NPh2Si(Me3Si)2SiK·18-crown-6 was converted to a magnesium silanide and further on to Et2NPh2Si(Me3Si)2Si-substituted ziroconocene and hafnocene chlorides. In addition, an example of a silanide containing both Et2NPh2Si and FPh2Si groups was prepared with moderate selectivity. Also, the analogous germanide Et2NPh2Si(Me3Si)2GeK·18-crown-6 could be obtained. [ABSTRACT FROM AUTHOR]

Three new organosilicon compounds based on dithienosilole (DTSi) were synthesized in good yields. We report the optical and electrochemical properties of the resulting derivatives. We find that these compounds absorb the light in the ultraviolet and blue light range, and they exhibit luminescence in almost the entire range of visible light. After electropolymerization were significantly lowered, the values of the energy gap (even 1.51 eV for P2) and the ionization potential of the polymers were compared to monomers. Optoelectronic properties of the obtained compounds suggest that these derivatives of DTSi may be good candidates as the emissive layers in white organic light-emitting diodes (WOLEDs), which would reduce the amount of layers. [ABSTRACT FROM AUTHOR]

Lantern Cage siloxanes with Janus‐type (unsymmetrical top and bottom) or symmetrical structure, which expand and shrink like Japanese lanterns, were synthesized and their structures and properties were revealed. When not in use, Japanese lanterns can be stored in shrunken form, while they can be expanded to accommodate candles inside; the Lantern cage is also expected to change its shape to include guest atoms or molecules with flexible siloxane framework. More information can be found in the Communication by M. Unno, R. Tanaka et al. on page 1683. [ABSTRACT FROM AUTHOR]

Carboxylic acid chlorides are useful substrates in organic chemistry. Many germanium analogues of carboxylic acid chloride have been synthesized so far. Nevertheless, all of the reported germathioacid chlorides use bidentate nitrogen ligands and contain germanium-nitrogen bonds. Our group synthesized germathioacid chloride, Ge(S)Cl{C6H3-2,6-Tip2}(Im-i-Pr2Me2), using N-heterocyclic carbene (Im-i-Pr2Me2). As a result of density functional theory (DFT) calculation, it was found that electrons are localized on sulfur, and the germanium-sulfur bond is a single bond with a slight double bond property. [ABSTRACT FROM AUTHOR]

The cover page of the journal "Angewandte Chemie" is presented.

Der Janus ‐ Würfel ist gelandet ‐ ‐ vielleicht folgt ein großer Schritt für die Materialwissenschaften. In ihrer Zuschrift auf S. 9482 ff. berichten M. Unno und Mitarbeiter über die Synthese und Röntgen ‐ Kristallstruktur eines Octasilsesquioxans mit zwei verschiedenen Substituentenarten, das einem nanoskaligen Janus ‐ Partikel entspricht. Die beiden Würfelhälften, ein Natriumcyclosiloxanolat und ein cyclisches Fluorsiloxan, werden durch eine neuartige Kreuzkupplung verknüpft. [ABSTRACT FROM AUTHOR]

The article describes the synthesis of octacarboxyphenyl functionalized cage, octakis[(p-carboxyphenyl)dimethylsilyl]silicate (OCPDS). According to the authors, the spherosilicate cage structure remains intact during the hydrolysis of octakis[dimethyl(4-tribromomethylphenyl)-silyl]silicate. They add that OCPDS shows lower thermal decomposition temperature due to easier decomposition of the carboxyphenyl groups than the tolyl groups.