Langmuir–Blodgett films composed of amphiphilic double-decker shaped polyhedral oligomeric silsesquioxanes

Küçük, Asuman Çelik; Matsui, Jun; Miyashita, Tokujı

doi:10.1016/j.jcis.2010.12.033

Cited by 45 publications

(39 citation statements)

References 33 publications

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“…At the same time, chemists are looking for synthetic routes exploiting among others hydrosilylation reaction to obtain novel, functionalized Si-based reagents with a specific structure such as silsesquioxanes. [17][18][19][20][21][22][23][24][25][26][27] While hydrosilylation of olefins with silanes has been widely studied, [3,28] the reports on T 8 silsesquioxanes are limited [5,6,[29][30][31][32][33][34] and for double-decker systems of both closed (D 2 T 8 [4,19,25,[35][36][37] ) and opened (M 4 T 8 [38][39][40][41][42][43] ) structure even more scant. [5] Cage-like derivatives have driven much attention due to specific physicochemical properties (governed by the nature of their silicate rigid core and by the number and type of functional groups attached to it) affecting directions of their broad applications from material chemistry to medicine.…”

Section: Introductionmentioning

confidence: 99%

“…[5] Cage-like derivatives have driven much attention due to specific physicochemical properties (governed by the nature of their silicate rigid core and by the number and type of functional groups attached to it) affecting directions of their broad applications from material chemistry to medicine. [39,40,43] These systems and their derivatives with phosphonic acid were reported to form Langmuir-Blodgett film and were investigated in the matter of proton conductivity, formation of hydrogen bonds as well as coordination of K + ions. [6][7][8][9][10][11] Nowadays, scientists are mostly focused on the investigation of possible modifications and further use of cubic T 8 cages and, for the last decade, doubledecker silsesquioxane (DDSQ) systems too.…”

Section: Introductionmentioning

confidence: 99%

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Highly Efficient Route for the Synthesis of a Novel Generation of Tetraorganofunctional Double‐decker Type of Silsesquioxanes

et al. 2019

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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.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Highly Efficient Route for the Synthesis of a Novel Generation of Tetraorganofunctional Double‐decker Type of Silsesquioxanes

et al. 2019

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“…Notably, the introduction of POSS into the main chains influenced the dense pack of the polymer chains, resulting in the depression in glass transition temperatures ( T g s). In the past years, the studies on the difunctional POSS macromers of DDSQ have provoked considerable interest . In most of the previous reports, the difunctional POSS macromers were introduced into the main chains of polymers via various step‐growth polymerization approaches .…”

Section: Introductionmentioning

confidence: 99%

“…[32][33][34][35][36][37][38][39][40][41][42][43][44][45] In most of the previous reports, the difunctional POSS macromers were introduced into the main chains of polymers via various step-growth polymerization approaches. [32][33][34][35][36][37][38][39][40][41][42][43][44][45] Generally, step-growth polymerizations only result in the introduction of POSS cages into the main chains of heterochain polymers. More recently, Zheng reported the synthesis of the organic-inorganic poly(N-isopropylacrylamide) (PNIPAAm) copolymers with POSS in the main chains via the combination of polycondensation and reversible addition fragmentation chain transfer (RAFT) polymerizations.…”

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confidence: 99%

Organic–inorganic poly(N‐vinylpyrrolidone) copolymers with double‐decker silsesquioxane in the main chains: Synthesis, glass transition, and self‐assembly behavior

Liu

Zheng

2016

J. Polym. Sci. Part A: Polym. Chem.

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An organic–inorganic copolymer with polyhedral oligomeric silsesquioxane (POSS) and xanthate moieties in the main chain was synthesized via the polycondensation between 3,13‐di(2‐bromopropionate)propyl double‐decker silsesquioxane (DDSQ) and 1,4‐di(xanthate potassium)butane. This hybrid copolymer was used as the macromolecular chain transfer agent to obtain the organic–inorganic poly(N‐vinylpyrrolidone) (PVPy) copolymers via a reversible addition fragmentation chain transfer/macromolecular design via the interchange of xanthates (RAFT/MADIX) polymerization approach; the polymerization behavior of N‐vinyl pyrrolidone was investigated by means of gel permeation chromatography. It was found that the polymerization was in a living and controlled manner. Transmission electron microscopy (TEM) showed that the organic–inorganic PVPy copolymers with DDSQ in the main chains were microphase‐separated in bulks. Compared to plain PVPy, the organic–inorganic PVPy copolymers displayed the decreased glass transition temperatures (Tgs); the decreased Tgs are attributable to the effect of the introduced DDSQ cages on the packing of PVPy chains as evidenced by means of Fourier transform infrared spectroscopy (FTIR). In water, the organic–inorganic PVPy copolymers can self‐assemble into the spherical nano‐objects with the size of 20–50 nm in diameter. In the self‐assembled nano‐objects, the aggregates of the hydrophobic DDSQ constituted the cores of the polymeric micelles whereas the PVPy chains between the DDSQ behaved as the coronas of the polymeric micelles. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2949–2961

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“…We have reported that DDSQ with two (2DEGDDSQ) or four DEG (4DEGDDSQ) units form a uniform monolayer at the airwater interface. 6 Moreover, a unique rod-like assembly was formed when a urethane group was attached at the end of DEG groups in 2DEGDDSQ. 7 FT-IR spectroscopy indicated that strong intermolecular hydrogen bonding between the urethane groups induced the formation of a rod-like assembly.…”

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confidence: 99%

Monolayer Property of “Core–Coronae” Type Hybrid Amphiphile with Four Hydrogen-bonding Groups at Air–Water Interface

Matsui

Küçük²,

Miyashita³

2012

Chemistry Letters

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A "corecoronae" type hybrid amphiphile, which contains urethane unit in the coronae was synthesized, and the monolayer property was studied. The hybrid amphiphile formed a liquidlike monolayer at the airwater interface. The urethane groups formed intramolecular hydrogen bonds.Recently, organicinorganic hybrid materials have attracted considerable attention because they show unique mechanical and physical properties.1 The organization of organic fragments and inorganic fragments at molecular levels is an important factor that determine their unique properties.2 The bottom-up approach such as layer-by-layer 3 and LangmuirBlodgett (LB) techniques can be used to assemble hybrid materials. 4 For manipulating molecules using LB technique, amphiphilic materials are required.5 Recently, we reported hybrid amphiphilic materials based on double-decker-shaped silsesquioxanes (DDSQ). 68 The hybrid amphiphiles are "corecoronae" type because they are composed of DDSQ as an inorganic core and di(ethylene glycol) (DEG)s as the organic coronae. We have reported that DDSQ with two (2DEGDDSQ) or four DEG (4DEGDDSQ) units form a uniform monolayer at the airwater interface.6 Moreover, a unique rod-like assembly was formed when a urethane group was attached at the end of DEG groups in 2DEGDDSQ.7 FT-IR spectroscopy indicated that strong intermolecular hydrogen bonding between the urethane groups induced the formation of a rod-like assembly. However, the properties of urethaneattached 4DEGDDSQ assembly were not reported. In this study, we synthesized 4DEGNHDDSQ, which contains a urethane group at the end of four DEG units. The urethane group was selected because urethane groups form strong hydrogen bonds. The effect of the hydrophilic end group on the monolayer property of the four-armed corecoronae-type amphiphile was studied.4DEGNHDDSQ was synthesized by direct hydrosilylation of DDSQ with di(ethylene glycol) vinyl ether, followed by the reaction of OH groups with ethyl isocyanate (Scheme 1). 9Direct hydrosilylation was carried out in toluene at 0°C using platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Karstedt's catalyst; 50 ppm) as catalyst. The crude product was purified by silica gel column chromatography eluted with THF/n-hexane. The purified compound was dissolved in toluene at 0°C and stirred in an argon atmosphere. Then, ethyl isocyanate was added dropwise into the reaction mixture. The reaction was carried out at room temperature for 1 day. Unreacted isocyanate was removed by evaporation. Figure 1 shows the FT-IR spectra of the initial compounds (4DEG DDSQ) and the obtained compound (4DEGNHDDSQ). The OH peak related to DEG units at 3444 cm ¹1 band shifts at 3343 cm ¹1 , which is attributed to the NH vibration in 4DEGNH DDSQ. Moreover, peaks related to the carbonyl peak appeared at 1720 and 1707 cm ¹1 ( Figure S2).10 1 H NMR spectrum of 4DEGNHDDSQ was recorded in CDCl 3 . The 1 H NMR spectrum of the product indicated the presence of NH (4.7 ppm) and CH 3 (1.1 ppm) and the disappearance of OH (2.0 ppm) ( Figure S1). 10...

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Langmuir–Blodgett films composed of amphiphilic double-decker shaped polyhedral oligomeric silsesquioxanes

Cited by 45 publications

References 33 publications

Highly Efficient Route for the Synthesis of a Novel Generation of Tetraorganofunctional Double‐decker Type of Silsesquioxanes

Highly Efficient Route for the Synthesis of a Novel Generation of Tetraorganofunctional Double‐decker Type of Silsesquioxanes

Organic–inorganic poly(N‐vinylpyrrolidone) copolymers with double‐decker silsesquioxane in the main chains: Synthesis, glass transition, and self‐assembly behavior

Monolayer Property of “Core–Coronae” Type Hybrid Amphiphile with Four Hydrogen-bonding Groups at Air–Water Interface

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