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

Kunthom, Rungthip; Takeda, Nobuhiro; Unno, Masafumi

doi:10.3390/molecules24234252

Cited by 8 publications

(3 citation statements)

References 41 publications

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“…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 ].…”

Section: Resultsmentioning

confidence: 86%

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

et al. 2021

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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.

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Section: Resultsmentioning

confidence: 86%

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

et al. 2021

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“…The solid was prepared through a simple single-step reaction, starting with the TetraSilanolPhenyl POSS (PhPOSS) and the terbium and europium acetate precursors. This partially condensed POSS [100][101][102][103][104][105] possesses a pre-formed cubic cage with four diametrically opposite silanol groups (Figure S1) that are able to coordinate the two different lanthanide ions simultaneously. An analogous solid bearing in the structure Tb 3+ ions was also prepared (Tb-PhPOSS).…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Novel Luminescent Double-Decker Silsesquioxanes Based on Partially Condensed TetraSilanolPhenyl POSS and Tb3+/Eu3+ Lanthanide Ions

2022

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In this study, novel lanthanide-containing double-decker polyhedral oligomeric silsesquioxanes (POSS) were prepared by combining the partially condensed TetraSilanolPhenyl POSS with terbium (Tb3+) and europium (Eu3+) ions. This open-cage POSS possesses four diametrically opposite silanol groups that are able to coordinate, under mild conditions, different luminescent ions through a simple corner-capping method. The two metal-containing POSS functionalized with Tb3+ and with an equimolar combination of Tb3+ and Eu3+ show a completely condensed structure with different luminescent properties. Their emission features depend on the chemical nature of the metal ions incorporated in the framework. An improved stokes shift was detected in the bimetallic compound containing both the Tb3+ and Eu3+ ions, promoted by the occurrence of a Tb3+→Eu3+ energy transfer mechanism. These characteristics identify this metal-functionalized silica platform as a potential candidate for the development of novel luminescent devices.

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“…Octaarylsilsesquioxanes with reactive or non-reactive organic groups were synthesized from cyclotetrasiloxanetetraols and their sodium salts in the presence of ammonium catalysts [ 17 ]. Unsymmetrical silsesquioxane double-deckers of new types [ 17 , 18 , 19 , 20 , 21 , 22 ], the basket [ 23 ] and butterfly types [ 24 ], or siloxane cages were reported to be obtained by simple hydrolytic condensations of two cyclosiloxanes with an organomonosilane. They can be building blocks for diverse applications since materials based on them should have low dielectric constants and excellent thermal stability.…”

Section: Introductionmentioning

confidence: 99%

The Influence of HCl Concentration on the Rate of the Hydrolysis–Condensation Reaction of Phenyltrichlorosilane and the Yield of (Tetrahydroxy)(Tetraphenyl)Cyclotetrasiloxanes, Synthesis of All Its Geometrical Isomers and Thermal Self-Condensation of Them under “Pseudo”-Equilibrium Conditions

et al. 2021

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The rate of hydrolysis–condensation reaction of phenyltrichlorosilane in water-acetone solutions and the product yields were shown to significantly depend on the concentration of HCl (CHCl) in the solutions. The main product of the reaction was all-cis-(tetrahydroxy)(tetraphenyl)cyclotetrasiloxane. This was different from the earlier published results of analogous reactions of m-tolylSiCl3, m-ClPhSiCl3, and a-naphtylSiCl, in which some products of other types were formed. For example, trans-1,1,3,3-tetrahydroxy-1,3-di-α-naphtyldisiloxane was obtained in the case of a-naphtylSiCl3. All-cis-(tetrahydroxy)(tetraphenyl)cyclotetrasiloxane was treated in acetone with HCl to give the other three geometric isomers (cis-cis-trans-, cis-trans-, and all-trans-). The thermal self-condensation of these four isomers under “pseudo”-equilibrium conditions (under atmospheric pressure) was investigated in different solvents, in quartz or molybdenum glass flasks. The compositions of the products were monitored by APCI-MS and 29Si NMR spectroscopy. It was shown that all-cis- and cis-cis-trans-isomers in toluene or anisole mostly gave the cage-like Ph-T8,10,12,14 and uncompleted cage-like Ph-T10,12OSi(HO)Ph compounds. In contrast to these two isomers, the cis-trans–isomer in toluene mainly formed dimers with the loss of one or two molecules of water. However, in acetonitrile, significant amounts of Ph-T10,12 and Ph-T10,12OSi(HO)Ph species were formed along with the dimers. All-trans-isomer did not enter into the reaction at all.

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

Cited by 8 publications

References 41 publications

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

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

Synthesis of Novel Luminescent Double-Decker Silsesquioxanes Based on Partially Condensed TetraSilanolPhenyl POSS and Tb3+/Eu3+ Lanthanide Ions

The Influence of HCl Concentration on the Rate of the Hydrolysis–Condensation Reaction of Phenyltrichlorosilane and the Yield of (Tetrahydroxy)(Tetraphenyl)Cyclotetrasiloxanes, Synthesis of All Its Geometrical Isomers and Thermal Self-Condensation of Them under “Pseudo”-Equilibrium Conditions

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