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 47 publications

(33 citation statements)

References 179 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Section: Introductionmentioning

confidence: 99%

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

2022

Self Cite

View full text Add to dashboard Cite

show abstract

“…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

Self Cite

View full text Add to dashboard Cite

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.

show abstract

“…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

View full text Add to dashboard Cite

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.

show abstract

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 47 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

Contact Info

Product

Resources

About