Progress in the self-assembly of organic/inorganic polyhedral oligomeric silsesquioxane (POSS) hybrids

Mohamed, Mohamed Gamal; Kuo, Shiao‐Wei

doi:10.1039/d2sm00635a

Cited by 52 publications

(36 citation statements)

References 179 publications

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“…The self-assembly of linear diblock copolymers in the bulk state, forming body-centered cubic (BCC), hexagonal-packing cylinder (HEX), double-gyroid (DG), and lamellae (LAM) structures, mediated by the interaction parameter (χ), volume fraction ( f ), and molecular weight ( N ), is being investigated widely because of their potential applications in nanopatterns, nanocomposites, drug delivery, and electronic and photonic devices. − Blending diblock copolymers with homopolymers, copolymers, nanoparticles, and organic–inorganic hybrids to vary the volume fractions and interaction parameters, mediated by hydrogen-bonding interactions, is another simple approach toward fabricating various self-assembled structures. − Recently, Frank–Kasper (FK) phases, including A15, σ, C14, and C15 phases, have also been observed in the phase diagrams of diblock copolymers through both experimental studies and theoretical predictions. − …”

Section: Introductionmentioning

confidence: 99%

Mesoporous Phenolic/POSS Hybrids Induced by Microphase Separation Arising from Competitive Hydrogen Bonding Interactions

2022

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We used ring-opening living polymerization to synthesize various linear poly(ethylene oxide−b−caprolactone) (PEO-b-PCL, EC) diblock copolymers featuring PCL blocks of various molecular weights and prepared phenolic resins with various double-decker silsesquioxane (DDSQ) cage compositions in the form of phenolic/DDSQ (PDDSQ) hybrids. Upon forming PDDSQ/EC blends, competitive hydrogen bonding of the phenolic OH units of PDDSQ occurred with both ether units of the PEO block and C�O units of the PCL block, with the fraction of hydrogen-bonded C�O groups increasing upon increasing the PDDSQ compositions but decreasing upon increasing the molecular weight of the PCL block in EC diblock copolymers. Small-angle X-ray scattering revealed the self-assembled structures and corresponding phase diagram of these PDDSQ/EC blends after thermal polymerization at 150 °C, with the d-spacing increasing upon increasing the molecular weight of PCL block in the EC diblock copolymers. After removal of the EC diblock copolymer template, we obtained mesoporous phenolic/DDSQ hybrids possessing high surface areas and pore volumes, with the highly ordered mesoporous structures featuring double-gyroid, hexagonal-packing cylindrical, spherical, and even Frank−Kasper (FK) structures depending on the molecular weight of PCL block and the content of the PPDSQ hybrid. Overall, this study provides a general principle for obtaining mesoporous double-gyroid and FK phases mediated by diblock copolymer compositions through competitive hydrogen-bonding interactions.

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Section: Introductionmentioning

confidence: 99%

Mesoporous Phenolic/POSS Hybrids Induced by Microphase Separation Arising from Competitive Hydrogen Bonding Interactions

2022

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“…Hybrid porous materials incorporating polyhedral oligomeric silsesquioxane (POSS) units are interesting because of their outstanding mechanical and thermal characteristics and high surface areas [ 42 , 43 , 44 , 45 , 46 , 47 ]. POSS derivatives are nanosized compounds having diameters of 1–3 nm, with regulated porosity and defined structures [ 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 ]. Many POPs synthesized from POSS derivatives have exhibited remarkable thermal stabilities, fluorescence characteristics, and surface areas [ 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 ].…”

Section: Introductionmentioning

confidence: 99%

An Ultrastable Porous Polyhedral Oligomeric Silsesquioxane/Tetraphenylthiophene Hybrid as a High-Performance Electrode for Supercapacitors

et al. 2022

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In this study, we synthesized three hybrid microporous polymers through Heck couplings of octavinylsilsesquioxane (OVS) with 2,5-bis(4-bromophenyl)-1,3,4-oxadiazole (OXD-Br2), tetrabromothiophene (Th-Br4), and 2,5-bis(4-bromophenyl)-3,4-diphenylthiophene (TPTh-Br2), obtaining the porous organic–inorganic polymers (POIPs) POSS-OXD, POSS-Th, and POSS-TPTh, respectively. Fourier transform infrared spectroscopy and solid state 13C and 29Si NMR spectroscopy confirmed their chemical structures. Thermogravimetric analysis revealed that, among these three systems, the POSS-Th POIP possessed the highest thermal stability (T5: 586 °C; T10: 785 °C; char yield: 90 wt%), presumably because of a strongly crosslinked network formed between its OVS and Th moieties. Furthermore, the specific capacity of the POSS-TPTh POIP (354 F g−1) at 0.5 A g−1 was higher than those of the POSS-Th (213 F g−1) and POSS-OXD (119 F g−1) POIPs. We attribute the superior electrochemical properties of the POSS-TPTh POIP to its high surface area and the presence of electron-rich phenyl groups within its structure.

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“…Nanosized silsesquioxane [RSiO 1.5 ] n units bridge a gap between organics and inorganics with their pure inorganic Si-O-Si main chain, surrounded by various organic substituents [ 1 , 2 , 3 , 4 , 5 ]. Silsesquioxanes are often regarded as unique molecular models of silica, both for investigations into surface phenomena [ 6 ] and heterogeneous catalysis [ 7 ].…”

Section: Introductionmentioning

confidence: 99%

A Novel Family of Cage-like (CuLi, CuNa, CuK)-phenylsilsesquioxane Complexes with 8-Hydroxyquinoline Ligands: Synthesis, Structure, and Catalytic Activity

et al. 2022

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The first examples of metallasilsesquioxane complexes, including ligands of the 8-hydroxyquinoline family 1–9, were synthesized, and their structures were established by single crystal X-ray diffraction using synchrotron radiation. Compounds 1–9 tend to form a type of sandwich-like cage of Cu4M2 nuclearity (M = Li, Na, K). Each complex includes two cisoid pentameric silsesquioxane ligands and two 8-hydroxyquinoline ligands. The latter coordinates the copper ions and corresponding alkaline metal ions (via the deprotonated oxygen site). A characteristic (size) of the alkaline metal ion and a variation of characteristics of nitrogen ligands (8-hydroxyquinoline vs. 5-chloro-8-hydroxyquinoline vs. 5,7-dibromo-8-hydroxyquinoline vs. 5,7-diiodo-8-hydroxyquinoline) are highly influential for the formation of the supramolecular structure of the complexes 3a, 5, and 7–9. The Cu6Na2-based compound 2 exhibits high catalytic activity towards the oxidation of (i) hydrocarbons by H2O2 activated with HNO3, and (ii) alcohols by tert-butyl hydroperoxide. Studies of kinetics and their selectivity has led us to conclude that it is the hydroxyl radicals that play a crucial role in this process.

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Progress in the self-assembly of organic/inorganic polyhedral oligomeric silsesquioxane (POSS) hybrids

Abstract: This Review describes recent progress in the self-assembly of organic/inorganic POSS hybrids derived from mono-, di-, and multi-functionalized POSS cages. We highlight the self-assembled structures and physical properties of giant...

Cited by 52 publications

References 179 publications

Mesoporous Phenolic/POSS Hybrids Induced by Microphase Separation Arising from Competitive Hydrogen Bonding Interactions

Mesoporous Phenolic/POSS Hybrids Induced by Microphase Separation Arising from Competitive Hydrogen Bonding Interactions

An Ultrastable Porous Polyhedral Oligomeric Silsesquioxane/Tetraphenylthiophene Hybrid as a High-Performance Electrode for Supercapacitors

A Novel Family of Cage-like (CuLi, CuNa, CuK)-phenylsilsesquioxane Complexes with 8-Hydroxyquinoline Ligands: Synthesis, Structure, and Catalytic Activity

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