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International audience; The attachment and dissociation of a proton from a water molecule and the proton transfers at solidliquid interfaces play vital roles in numerous biological, chemical processes and for the development of sustainable functional materials for energy harvesting and conversion applications. Using first-principles computational methodologies, we investigated the protonated forms of polyhedral oligomeric silsesquioxane (POSS-H+) interacting with water clusters (Wn, where n = 1-6) as a model to quantify the proton conducting and localization ability at solid-liquid interfaces. Successive addition of explicit water molecules to POSS-H+ shows that the assistance of at least three water molecules is required to dissociate the proton from POSS with the formation of an Eigen cation (H9O4+), whereas the presence of a fourth water molecule highly favors the formation of a Zundel ion (H5O2+). Reaction pathway and energy barrier analysis reveal that the formation of the Eigen cation requires significantly higher energy than the Zundel features. This confirms that the Zundel ion is destabilized and promptly converts in to Eigen ion at this interface. Moreover, we identified a Grotthuss-type mechanism for the proton transfer through a water chain close to the interface, where symmetrical and unsymmetrical arrangements of water molecules around H+ of protonated POSS-H+ are involved in the conduction of proton through water wires where successive Eigen-to-Zundel and Zundel-to-Eigen transformations are observed in quick succession.

A series of ethylene-propylene-diene-terpolymer (EPDM)/polyhedral oligomeric silsesquioxane (POSS) composites at different percentage of POSS were prepared and subjected to γ-irradiation. Both irradiated and non-irradiated EPDM and composites were investigated by the means of thermal analysis to verify if the presence of POSS molecules is able to reduce the oxidation level of free radicals generated during the degradation and to evaluate the effects of the irradiation. EPDM composites at 1, 3 and 5 mass% of POSS were thus degraded in a thermogravimetric (TG) balance in dynamic heating conditions (25–700 °C), in both inert and oxidative atmosphere by flowing nitrogen and air respectively. Thermal characterization was then completed by carrying out Differential Scanning Calorimetry (DSC) analysis from sub-ambient to better highlight the melting of the polymer and polymer composites occurring just above the room temperature. FTIR spectroscopy was also performed for the prepared samples to check the presence of the molecular filler in the composites and for the TG’s residue at 700 °C, in order to evaluate its nature. DSC and TGA parameters were detected and discussed to have information about the effect of the degradation’s environment, the effect of irradiation on polymer stabilization and the effect of POSS content in the polymer matrix.

Fluorinated polyhedral oligomeric silsesquioxane (F-POSS) is one of the most popular candidates at present for superhydrophobic coating. Because of its ultralow surface energy, F-POSS has usually been dissolved with expensive fluoro-solvents, and the melting temperature of F-POSS is not high (122–140 °C), which will cause its loss during use. So trying to polymerize/crosslink F-POSS molecules and/or directly graft F-POSS to substrate is important. In this work, we report the SI-eATRP grafting of methacryl POSS (MA-POSS) on cotton and the subsequent amine catalyzed thiol-methacrylate Michael addition reaction of poly(MA-POSS) with 1H, 1H, 2H, 2H-perfluorododecyl-1-thiol (PFDT) for the fabrication of a durable poly(MA-POSS)-PFDT coating. The cotton fabric coated with poly(MA-POSS) was nearly superhydrophobic after 4 h of SI-eATRP process under potentiostatic condition of −0.40 V. Although the water contact angle (WCA) was ~148°, water droplets tended to adhere to the cotton fabric surface even when the fabric was turned upside down. After fluorination, WCA was increased to ~160°, and water drops could slide off when the fabric was slightly tilted. The sliding angle (SA) was ~10°. The as-prepared poly(MA-POSS)-PFDT coating was durable against repeated washing and physical abrasion. After 30 accelerated washing cycles (equals to 150 home laundering cycles), the coated fabric still showed superhydrophobicity. After 800 abrasion cycles over sandpaper, the WCA was still as high as 149°. In addition, the coated fabric had self-healing ability and could restore its superhydrophobicity after plasma etching through heat treatment. After 10 cycles of plasma etching and heat-induced healing process, the WCA of the coated fabric kept at ~154°. Such a durable superhydrophobic fabric coating may find applications in the development of functional clothing for a variety of purposes.

Flutamide is a man-made non-steroidal anti-androgen drug that is extensively used for the prostate cancer therapy. Though the drug has a higher benefit ratio in treating cancer, it also exhibits certain lethal side effects to humans. It acts as an environmental pollutant instigating water pollution and aquatic organism damage by interfering in their reproductive cycle and its effect on aquatic life is a major concern. Hence, it is mandatory to detect the presence of this nitro-aromatic compound. For the effective determination of this analyte, gold modified Polyhedral Oligomeric Silsesquioxane (abbreviated as POSS-S-Au) based organic-inorganic hybrid material as chemical modifier has been used. This material synthesized via a hydrolysis-condensation reaction technique followed by a phase transfer method is utilized for the first time in the electrochemical determination of anti-cancer drug. The as-synthesized nanomaterial has been subjected to various Physio-chemical characterization and the Fourier Transform- Infrared Spectroscopy (FT-IR) spectra confirm the presence of -SH organic group and Si-O-Si stretch. X-ray Photoelectron Spectroscopy (XPS) spectra affirms the presence of silicon, oxygen, gold, and Sulphur owing to the introduction of gold through the thiolation of silicate core. The fabricated sensor showed excellent electro-catalytic activity for detecting flutamide with limit of detection (LOD) of 0.12 μM, and higher sensitivity of around 0.048 μA/μM.

Control of the shape and uniformity of colloid particles is essential for realizing their functionality in various applications. Herein, we report a facile approach for the synthesis of narrowly dispersed anisotropic microparticles with well-defined raspberry-like and golf ball-like surface patterns. First, we demonstrate that hybrid raspberry-like particles can be achieved through a one-pot polymerization method using glycidyl polyhedral oligomeric silsesquioxane (GPOSS) and pentaerythritol tetra(3-mercaptopropionate) (PETMP) as monomers. Varying the polymerization parameters such as catalyst loading, monomer concentration, and the molar ratio of monomers, we are able to regulate the sizes and surface protrusion numbers of these raspberry-like microparticles. The formation mechanism is attributed to a competition balance between thiol-epoxy reaction and thiol-thiol coupling reaction. The former promotes rapid formation of large core particles between PETMP and GPOSS droplets (which can serve as core particles), while the latter allows for generation of surface protrusions by PETMP self-polymerization, leading to the formation of raspberry-like surface patterns. Based on the different POSS contents in the surface protrusions and cores of the raspberry-like microparticles, we demonstrate that they can be used as precursors to produce microporous silica (sub)microparticles with golf ball-like morphology via pyrolysis subsequently. Overall, this work provides a facile yet controllable approach to synthesize narrowly dispersed anisotropic microparticles with diverse surface patterns.

Silsesquioxane-based materials are garnering considerable attention due to their unique structural and electronic properties which enable use in diverse fields of study. In this article, we investigate a series of hybrid oligomeric materials comprising a silsesquioxane (SQ) backbone linked by conjugated organic cross-linkers and assess their photophysical properties in the steady state absorption and emission realms. Silsesquioxanes improve the thermal and photo stabilities of the organic components, offer enhancements in the molar extinction coefficients of absorption, and have a significant influence on their emission properties. We used Heck cross-coupling reactions to build oligomers with a vinyl/phenylSQ cage backbone linked with a series of different cross-linkers including 2,7-dibromo-9-fluorenone, 2,7-dibromo-9,9-dimethylfluorene, 1,4-dibromo-2,5-dimethoxybenzene, 2,5-dibromopyridine, 2,6-dibromopyridine, 2,3-dibromothiophene, 2,5-dibromothiophene, and 2,5- dibromothieno [3,2-b]thiophene. Each of these linkers showed reasonable conversion to oligomers and exhibited a wide array of fluorescence quantum yield and shifts in the absorption and emission spectra dependent on the variations in substitution position. We confined the study to explore the overall steady state spectral properties of these synthesized hybrid materials in their solution phases. Understanding the basic photophysical processes in these materials will pave the way towards their use in photovoltaic or electroluminescence applications.

International audience; We report here the synthesis, structure, luminescence, and magnetic properties of three new cage-like tetranuclear silsesquioxanes (Et 4 N) 2 [(PhSiO 1..5) 8 (Y 0.75 Dy 0.25 O 1.5) 4 (O)(NO 2.5) 6 (EtOH) 2 (MeCN) 2 ] and (Cat) 2 [(PhSiO 1.5) 8 (DyO 1.5) 4 (O)(NO 2.5) 6 (EtOH) 2 (MeCN) 2 ] (Cat=Et 4 N or Ph 4 P). They present a characteristic greenyellow emission. The Y 3+ /Dy 3+ compound displays in addition a field-induced Single Molecule Magnet (SMM) behavior making it the first reported bifunctional magneto-luminescent silsesquioxane.

In this study, the compatibilization effects of triglycidylisobutyl polyhedral oligomeric silsesquioxane (TEpPOSS) on biodegradable poly(lactic acid) (PLA)/thermoplastic polyurethane (TPU) blends were investigated. All blends were prepared via melt blending and PLA/TPU (80/20, 70/30, 50/50 wt%) ratio was selected as the experimental parameter. In order to predict the selective localization of TEpPOSS thermodynamically, wetting coefficient were determined by means of surface energy measurements. Morphological analyses were carried out by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Moreover, rheological, mechanical, thermomechanical and thermal properties of the blends were performed via rheometer, universal tensile tester, dynamic mechanic analyses and differential scanning calorimeter (DSC), respectively. Morphological test results revealed that TEpPOSSs were mostly located at the interfaces of the PLA and TPU phases. According to the rheological studies, the interfacial interactions between PLA and TPU were improved with the addition of TEpPOSS, which resulted from the potential reactions between epoxy-carboxylic acid and/or epoxy-hydroxyl functional groups. The addition of TEpPOSS enhanced the mechanical properties of PLA/TPU blends. DSC test results revealed a decrease in the glass transition temperatures of PLA in the presence of TEpPOSS, which was an another indication of improved compatibility between PLA and TPU.

In this study, the multi-wall carbon nanotubes (MWCNTs) were grafted with Octa (propyl glycidyl ether) polyhedral oligomeric silsesquioxane (GOPOS) to form GOPOS-G-MWCNTs prior to use as an additive for improving the mechanical and the flame-retardant characteristics of the epoxy resin (EP). The surface of MWCNTs was also modified with a silane coupling agent before conducting the grafting reaction. The Fourier-transform infrared spectroscopy technique was applied to confirm the success of the grafting reaction. The epoxy-based composite materials were performed at room temperature using diethylenetriamine (DETA) as a hardener. Many characteristics of these materials were examined such as tensile strength, thermal stability, flammability, and fracture surface morphology. The presence of GOPOS-G-MWCNTs helped to reduce the total heat release, the peak of heat release rate (pHRR), and total smoke release by 68.68, 47.69, and 11.78%, respectively. While the tensile strength and fracture energy were also increased up to 30 and 102% when compared with virgin EP. The good dispersion of GOPOS-G-MWCNTs and char residue effect were considered as the main reasons for these improvements. A mechanism for enhancing flame-retardant behaviors of EP was also proposed .

This work describes the preparation and use of a polydimethylsiloxane sponge amino functionalized for the adsorption of copper in water. The sponge was structurally characterized by infrared spectroscopy and solid-state 29Si NMR, which indicated the presence of silsesquioxane units that acted as nodes on the PDMS chains and linked the functional groups to the network. Thermogravimetric analysis of the product showed good thermal stability, with the initial temperature of weight loss at 400 °C. The material displayed a high degree of swelling in polar solvent, presumably due the cavities. The presence of the amino group increases the adsorption of copper onto the surface of the sponge, with adsorption capacity of about 2.0 mmol (127 mg) per gram of material. The sponge shows promising results for environmental remediation with the removal of copper in water, as well as a simple utilization with no need of a separation process after metal adsorption.

This study reports intriguing features in the self-assembly of cage copper(II) silsesquioxanes in the presence of air. Despite the wide variation of solvates used, a series of prismatic hexanuclear Cu6 cages (1-5) were assembled under mild conditions. In turn, syntheses at higher temperatures are accompanied by side reactions, leading to the oxidation of solvates (methanol, 1-butanol, and tetrahydrofuran). The oxidized solvent derivatives then specifically participate in the formation of copper silsesquioxane cages, allowing the isolation of several unusual Cu8-based (6 and 7) and Cu6-based (8) complexes. When 1,4-dioxane was applied as a reaction medium, deep rearrangements occurred (with a total elimination of silsesquioxane ligands), causing the formation of mononuclear copper(II) compounds bearing oxidized dioxane fragments (9 and 11) or a formate-driven 1D coordination polymer (10). Finally, a "directed" self-assembly of sil- and germsesquioxanes from copper acetate (or formate) resulted in the corresponding acetate (or formate) containing Cu6 cages (12 and 13) that were isolated in high yields. The structures of all of the products 1-13 were established by single-crystal X-ray diffraction, mainly based on the use of synchrotron radiation. Moreover, the catalytic activity of compounds 12 and 13 was evaluated toward the mild homogeneous oxidation of C5-C8 cycloalkanes with hydrogen peroxide to form a mixture of the corresponding cyclic alcohols and ketones.

The gel polymer electrolytes (GPEs) with poly(acrylonitrile-polyhedral oligomeric silsesquioxane)/poly(vinylidene fluoride) (PAN-POSS/PVDF) blends as free-standing porous membrane and ionic liquid (IL) as absorption substance were successfully prepared. By tuning the content of PAN-POSS, the porosity and absorptivity of the blended membranes could be regulated. Due to the higher porosity and absorptivity, the ionic conductivity of GPEs with 15 wt% PAN-POSS reaches to 1.91 × 10−3 S cm−1 at 20 oC. Meanwhile, the electrolytes also show excellent mechanical properties, thermal stability, and fire resistance. More importantly, the high electrochemical window of 4.6 V (vs. Li/Li+) has been acquired and the testing cells with Li metal anode and LiFePO4 cathode show a tolerable rate performance. Such prepared GPEs are expected to be applied to lithium batteries with high safety and electrochemical performance.

Encapsulated atomic hydrogen in silsesquioxane cages is a promising candidate for applications in emerging technologies like spin-based quantum computing, magnetic field sensing, and atomic clock d...

The addition of methacrylate-functional polyhedral oligomeric silsesquioxane (MA-POSS) nanoparticles to styrene-butadiene rubber (SBR) composites was evaluated in terms of rheological, mechanical, and morphological properties. The aging process and cross-link density of rubber nanocomposites were examined in presence of MA-POSS. The MA-POSS could directly participate in the vulcanization reaction due to its methacrylate groups and its concentration affected the rheological and mechanical properties of rubber. The sulfur vulcanization characteristics of MA-POSS/SBR nanocomposites were determined by moving die rheometer. It was indicated that the addition of MA-POSS to SBR composites retarded the curing time and decreased the cross-link density. Due to an effective interaction between MA-POSS nanofiller and SBR matrix and excellent dispersion of POSS, the mechanical properties of nanocomposites were higher than those of the reference compound without MA-POSS. However, there was no significant change investigated in tensile retention in presence of MA-POSS. The presence and the random distribution of MA-POSS in SBR matrix was confirmed by TEM analysis. The cross-link densities of the composites, which were calculated using Flory–Rehner equation, decreased with increasing amount of POSS nanofiller. It was finally revealed that the thermal aging dramatically reduced the mechanical properties and cross-link density of MA-POSS/SBR nanocomposites.

Organosilsesquioxane hybrid materials are an important class of functional materials due to their tailorable functions and high thermal and optical stability. Recently, several studies showed that ...

Polyamide-polyhedral oligomeric silsesquioxane (PA-POSS) nanocomposites are prepared using eco-friendly surfactant-free dimer fatty acid polyamide with different wt% of POSS by a facile solvent casting method. The prepared biopolymer nanocomposites are investigated using transmission electron microscopy, scanning electron microscopy, atomic force microscopy to understand the structural orientation between POSS and polyamide. Thermogravimetric analysis indicates that the PA-POSS have better thermal stability as compared to that of pristine polymers. Differential scanning calorimetry shows a shift in glass transition temperature as the loadings of POSS increase in the polymer. Dielectric properties such as dielectric breakdown strength, dielectric permittivity, dielectric loss, and AC conductivity are performed on polymeric materials to investigate frequency dependent dielectric properties. Results showed that the thermal stability and dielectric permittivity of PA-POSS are 25% superior compared to pristine polyamides; such an enhancement may be due to the POSS being uniformly settled in nano-level by proper structural orientation of POSS with the polyamide throughout the polymer matrix. PA-POSS nanocomposites exhibiting improved dielectric properties can be explored for the fabrication of biocompatible polymeric film capacitors application.

An azido-terminated polyhedral oligomeric silsesquioxane (POSS) compound, octakis(azidopropyl-3-oxycarbonyl-1-decyl-10-thiopropyl-3-)POSS (OADTP), is synthesized and characterized. POSS-polytriazole (PTA) resins are prepared from an azide, an alkyne monomer, and OADTP. The toughening effect of OADTP on PTA resins is analyzed by impact performance test and electronic microscope characterization, and the thermal performance of resins is measured by thermogravimetric analysis and dynamic mechanical analysis. The results show that the addition of the POSS can improve the mechanical properties of PTA resins. The impact strength of POSS-PTA resins first increases and then decreases with the increase in the POSS compound, and the maximum one arrives at 54.8 kJ m−2 which increases by 44.2% as compared to 38 kJ m−2 of the PTA resin. A good thermal stability remains in POSS-PTA resins.

Within this work, a modified preparation of diethyl 4-azidobenzylphosphonate (L1) is presented and the family of 4- or 4'-azido-substituted aromatic phosphonate esters is increased by three new ligand platforms: diisopropyl 4-azidobenzylphosphonate (L2), diisopropyl ((4'-azido-[1,1'-biphenyl]-4-yl)methyl)phosphonate (L3), and diisopropyl 4-azido-2,3,5,6-tetrafluorobenzylphosphonate (L4), which exhibit an anomalous splitting of the N3 stretching vibrations. Subsequent coordination to the in situ generated RPOSS (polyhedral oligomeric silsesquioxane)-cage-supported lanthanide precursors [(Ln{RPOSS})2(THF)m] (P1-P6) (Ln = La, Nd, Dy, Er; R = iBu, Ph; m = 0, 1) yields complexes of the general formula [Ln{RPOSS}(L1-L4)n(S1)x(THF)m] (1-30) (n = 2, 3; x = 0, 1; m = 0-2) retaining the azide unit for future semiconductor surface immobilization. Because the latter compounds are mostly oils or viscous waxes, preliminary solution-state structure elucidations via DOSY-ECC-MW estimations have been carried out which are in accordance with 1H NMR integral ratios as well as solid-state structures, where available. Moreover, the optical properties of the Nd, Dy, and Er derivatives of complexes 1-30 are examined in the visible and NIR spectral regions, where applicable.

Thermally stable dual emission followed by white-light luminescence from hybrid materials is reported. Hybrid films were prepared with a spin-coating method with the mixture solution containing tetraphenylethene (TPE)-integrated polyhedral oligomeric silsesquioxane (POSS) and poly[2-methoxy-5-(2′-ethylhexyloxy)-1, 4-phenylene vinylene] (MEH-PPV). TPE-tethered POSS (TPE-POSS) showed high compatibility with MEH-PPV. Therefore, homogeneous films with variable concentrations of TPE-POSS were obtained. Owing to good dispersion of rigid silica cubes into matrices, POSS-containing films demonstrated high thermal stability toward molecular rearrangement by annealing as well as pyrolysis, similar to conventional polymer hybrids. Furthermore, it was found that TPE-POSS was able to enhance emission efficiencies, probably by suppressing chain aggregation. By modulating introduction ratios of TPE-POSS, dual-emission properties followed by white-light luminescence composed of cyan and orange emissions from TPE-POSS and MEH-PPV, respectively, were accomplished. It should be noted that these color balances can be preserved even in the high-temperature region (425 K). Finally, white-light luminescent materials with thermal durability were obtained.

Thus far, research on silicon oxycarbide (SiOC, SiOnC4-n (0 ≤ n ≤ 4)) as an anode material for lithium-ion batteries (LIBs) has been focused on the quantity and quality of the carbon domains. This study, however, intends to present a new perspective in order to maximize the utilization of active sites by forming nanovoids in the Si–O–C domain. Structural native nanovoids were formed by introducing PSS-Octakis (dimethylsilyloxy) silsesquioxane (POSS) into the synthesis process of SiOC, and it was then utilized as anode materials of LIBs. Moreover, the effects of POSS on the chemical, structural, and electrochemical properties of SiOC were investigated by varying the content of POSS. It was determined that the addition of POSS could form nanovoids, reduce the free carbon region, decrease the electrical conductivity, and increase the oxygen-rich tetrahedral Si–O–C structure. Despite the reduced electrical conductivity, the porosity formed by the addition of POSS induced high output characteristics by enabling fast ion diffusion to the active SiOC site during the repetitive lithiation/delithiation processes. Furthermore, the nanovoids were found to be capable of improving the structural stability during charge/discharge processes through a buffering effect. Moreover, the increased oxygen-rich tetrahedral Si–O–C structure was able to maximize reversible capacity. Such structural change resulted in a high specific capacity of 980 mAh g−1 at a current density of 180 mA g−1 as well as improved rate capability. A high specific capacity of 412 mAh g−1 was obtained even at a high current density of 3600 mA g−1, and 94% of the initial capacity was maintained after 200 cycles at a current density of 360 mA g−1.

Analyzing the assembly patterns of multicomponent gelators is important for understanding their assembly rules and precisely manipulating their molecular structure to form a tailored multifunctional supramolecular gel. But the fast in situ recognition technology to infer whether the assembly pattern is a self-sorting or co-assembled system is lacking. For developing a widely applicable stable and sensitive fluorescent probe to infer assembly patterns, we design and synthesize the multiple peripheral functional group tetraphenylethene (TPE) modified well-defined cubic core polyhedral oligomeric silsesquioxane (POSS) three-dimensional (3D) dendrimer. POSS-TPE can form a thermally stable self-assembly structure after being incubated in a wide temperature range, and the resultant special thermally stable photoluminescence (PL) intensity provides a novel possibility of fluorescent probe. Then, POSS-TPE sensitively catches the mechanical stress changes of the confined space provided by the gel networks and infers the assembly patterns by comparing the mechanical stress change laws of a self-sorting or co-assembled system. So, the application of fluorescent probe in assembly fields is enlarged in this research. In the future, this widely applicable fluorescent probe will be helpful to develop supramolecular assembly materials consisting of multicomponent gels.

Nowadays, there is a need for a paradigm shift in material selection for surface coatings so as to meet the requirements of advanced systems. Polyhedral oligomeric silsesquioxanes (POSS) are three-dimensional networks with a silica-like core covered by an organic shell, a promising nanosized structure for organic coatings. The use of POSS structures in coating materials has experienced an almost erratic period over the past decade, mainly because of the synthesis of POSS being exclusive and, to some extent, expressive. However, there has been a big return to the use of POSS in coatings during the last years. Epoxy is best known for its versatility of usage as an organic coating. Hybrid organic–inorganic POSS nanostructures with unique properties are a complement to the epoxy for coating applications. The tailorable compatibility and considerable reactivity of POSS molecules towards organic groups have made them promising candidates for emerging multifunctional epoxy coatings. In this sense, the focus of this review is placed on POSS/epoxy nanocomposite coatings. The thermal, mechanical, anti-corrosion and dielectric properties of POSS/epoxy coatings have been comprehensively studied and discussed.

The mechanical behavior of polyethylene (PE) co-polymerized with polyhedral oligomeric silsesquioxane (POSS) was studied by using molecular simulations. Simulation configurations consisted of aligned PE chains with POSS attached to the central chain and amorphous PE chains with different content POSS. From the simulations with aligned PE chains with POSS, it was found that the method for reinforcement was due to dislocation pile-up at POSS, and above a critical stress the dislocations traverse the POSS causing a sawtooth variation in the load-displacement curve. The stress-strain curves for amorphous PE-POSS bulk showed distinct elastic and plastic straining stages. Plastic straining consisted of hardening and slipping segments attributed to dislocation pile-up and chain sliding. Computational results were used to develop a reinforcement model to describe the mechanical response of PE-POSS bulk under uniaxial tension.

There are numerous numbers of hypoxia-selective luminescent probes based on oxygen quenching of phosphorescence. We show a unique design for luminescent probes to detect hyperoxia utilizing hybrid networks consisting of aggregation-induced emission(AIE)-active dyes and disulfide linkers. At the initial state, emission from the AIE-active dyes is inducible by suppressing energy-consumable intramolecular motions in the hybrid matrices, while the decrease in intensity was detected by releasing molecular motions corresponded to bond scission at the disulfide linkers. Particularly, it was shown that this process selectively proceeds in hypoxia. As a result, positive luminescent signals were obtained in hyperoxia.

Polyhedral oligomeric silsesquioxane (POSS) is an inorganic-organic nanostructure. POSS nanocage possesses silica core and organic functionalities at corners. POSS has been familiarized with variou...

Significant efforts have been devoted to the photochemical CO2 reduction reaction (CO2RR) as a significant pathway for the development of renewable energy systems. However, the competitive hydrogen evolution reaction (HER) greatly impedes the fundamental understanding and industrial application of the CO2RR. Herein, we report polyhedral oligomeric silsesquioxane (POSS)-based porous organometallic polymers (POMPs) that are able to catalyze the photochemical CO2RR to produce syngas. Their surface area, CO2 adsorption ability, visible-light harvesting capacity and photoinduced electron–hole separation efficiency can be regulated by tuning the Re-bipyridine content in POMPs. Consequently, the effects of these properties on CO2RR and HER activities have been investigated and the surface area and electron transfer efficiency of these materials have been elucidated as the key points. Importantly, we also reveal the applicability of the developed strategy in designing new catalysts for the CO2RR.

Polyhedral oligomeric silsesquioxane (POSS) based starlike hybrid helical poly(phenyl isocyanide)s (PPIs) with well-defined structures were designed and prepared in this contribution. The POSS modified with Pd(II) complexes (POSS-Pd(II)) was firstly obtained. Then well-defined starlike hybrid helical PPIs with POSS cores were synthesized through the polymerization of phenyl isocyanide monomers using POSS-Pd(II) as the initiator. The polymerization proceeded in a living and controlled manner. Meanwhile, polymerization of chiral phenyl isocyanides with decyl chain modified pendant L- or D-alanine afforded optically active hybrid starlike helical PPIs with preferred handedness. What's more, amphiphilic starlike hybrid helical PPI block copolymers showing thermoresponses were easily obtained, and their self-assembly and thermo-responsive behaviours were studied. In addition, cross-linked hybrid helical PPIs were obtained via the transesterification reaction between pentafluorophenyl ester and cystamine. Benefitting from the essential chirality of the handed helical PPIs, the cross-linked hybrid PPIs showed excellent ability in the enantioselective crystallization of racemic compounds. The enantiomeric excess (ee) of the induced crystal of threonine could be up to 95%.

Evolving synthetic molecules toward complex structures is a major goal in supramolecular chemistry. Increasing the number of clips in a unimolecular multi-clip (UMC), although vital to elevate the complexity of supramolecular architectures, often prevents the UMC from forming host–guest complexes in the bulk phase. To overcome this difficulty, adaptive chemistry was applied to develop a novel adaptive unimolecular quaternary clip (Q-clip). The Q-clip is intrinsically amorphous, but self-organizes with exclusively 4 eq. of allosteric activators (NDI) to form the Q-clip : NDI4 complexes and a supramolecular lamellar structure in the bulk. The adaptive assembly is fast and allows us to locate the adaptive assembly area of Q-clip : NDI4 complexes in the amorphous Q-clip film. Our results provide new insights into the design of adaptive UMCs for the evolution toward complex structures and supramolecular functional materials.

Octasilsesquioxane cages with co-substituent characteristics were synthesized through polyhydrolytic–condensation reactions involving two mixed monomers, namely i-butyl(triethoxysilane) and organotrialkoxysilanes (e.g., phenyl, vinyl, ethyl, propyl, and 3-chloropropyl groups). Only mild and simple methods were required to obtain crystalline products as all products consisted octameric silsesquioxane (T8) cubes with normal distribution between i-butyl and other substituents. The formation was confirmed by NMR and ESI-MS spectra. The i-butyl group on the silane monomer was not only a controller to yield cage-like structural products with mixed substituents, but also their highly symmetrical Oh in the cubic Si–O core, which drives the product separation through crystallization. The crystalline structure of the products was validated by the correlation between the endothermic peak at the melting temperature (Tm) from the DSC analysis and sharp peaks observed in the XRD diffraction patterns.

A cost-effective and facile method was developed for the fabrication of two polyimide-based (PI-based) monoliths (pure PI monolith and hybrid PI monolith) with a hierarchically porous structure that avoids the shortcomings of traditional methods. In this case, the thermally induced phase separation (TIPS) method was used to prepare polyamic acid (PAA) monoliths for the first time, then PI-based monoliths were fabricated by thermal imidization. Through the introduction of octakis(glycidyldimethylsiloxy)octasilsesquioxane into the PAA prepared from 4,4′-oxydianiline and pyromellitic dianhydride, both the hydrophobicity and mechanical strengths of the PI-based monoliths were improved. Moreover, the resulting PI-based monoliths exhibited suitable permeability, homogeneous morphologies, and superior thermal stability. Adsorption tests demonstrated that the resulting hybrid PI monoliths exhibited better adsorption performance for organic solvents and silicone oil than the pure PI monolith. Furthermore, the surface of a polyhedral oligomeric silsesquioxane (POSS) hybridized PI (PI-co-POSS) monolith can be modified into a hydrophilic layer by reaction between the hydrophilic polymer and epoxy groups exposed on the surface. This indicates that PI-co-POSS monoliths have potential in liquid diode application to achieve oil–water separation.

In this work, octamercapto polyhedral oligomeric silsesquioxane (POSS-8SH) and octaphenol polyhedral oligomeric silsesquioxane (POSS-8Phenol) were successfully synthetized. POSS-8Phenol was added into the synthesis process of liquid thermoset phenolic resin (PR) to obtain POSS-modified phenolic resin (POSS-PR). Chemical structures of POSS-8SH, POSS-8Phenol, and POSS-PR were confirmed by FTIR and 1H-NMR. TG and DTG analysis under different atmosphere showed that char yield of POSS-PR at 1,000°C increased from 58.6% to 65.2% in N2, which in air increased from 2.3% to 26.9% at 700°C. The maximum pyrolysis temperature in air increased from 543°C to 680°C, which meant better anti-oxidation properties. XRD results confirmed both POSS-8Phenol and POSS-PR-generated crystalline SiO2 in air, which could explain the improvement of anti-oxidation properties. SEM showed that the POSS-PR had phase separation during curing process. Finally, carbon fiber fabric-reinforced POSS-PR (C-POSS-PR) was prepared to verify the anti-oxidation properties of POSS-PR.

Porous carbon is usually used as an anode material for fast sodium storage due to its exceptional pore structure and high electrical conductivity. Herein, lithium hepta(i-butyl)silsesquioxane trisilanolate (T7-Li) is directly pyrolyzed to fabricate ultrathin porous carbon nanosheet 3D architectures (PCNS) via a novel “in situ dual templating” strategy. On one hand, the organic groups of T7-Li act as carbon sources for PCNS, and on the other hand, the pyrolysis of the inorganic core in T7-Li can generate both silica nanoparticles which act as a template for the formation of a porous structure, and most significantly, lithium silicate nanosheets formed by the reaction of silica and lithium oxide which serve as an inducer for the formation of carbon nanosheets. Impressively, when applied as the anode material for Na-ion batteries, PCNS delivers an ultrafast capacity of 230.5 mA h g−1 at 10 A g−1. Furthermore, the Na-ion capacitor assembled using PCNS as both the anode and cathode delivers an extremely high energy density of 137 W h kg−1 at 3454 W kg−1. This work proposes a novel strategy for the synthesis of porous carbon nanosheets for fast sodium storage and provides more possibilities to enrich the application of metallasilsesquioxanes.

Tetra(3-mercaptopropyl)-silsesquioxanes with double-decker (DDSQ) or ladder nano-cores were easily prepared from the corresponding tetraallyl derivatives through fast and convenient thiol-ene reactions. An additional tetrathiol-DDSQ with more flexible arms was also synthesized in high yield from the corresponding tetrachloro-DDSQ derivative. The three novel tetrathiol silsesquioxanes described represent versatile building blocks for the preparation of hybrid organic-inorganic materials.

New luminescent cage-like tetranuclear silsesquioxanes [NEt4][(Ph4Si4O8)2(Tb3Eu)(NO3)4(OH)(EtOH)3(H2O)]·4(EtOH) (1) and [NEt4]2[(Ph4Si4O8)2(Tb2Eu2)(NO3)6(EtOH)2(MeCN)2]·4(MeCN) (2) present a tunable thermosensitive Tb3+-to-Eu3+ energy transfer driven by Tb3+ and Eu3+ emission and may be used as temperature sensors operating in the range 41–100 °C with excellent linearity (R2 = 0.9990) and repeatability (>95%). The thermometer performance was evidenced by the maximum relative sensitivity of 0.63% °C−1 achieved at 68 °C.

A porous silsesquioxane cage/porphyrin nanocomposite has been designed as a dual fluorescent probe for the sensing and adsorption of heavy metal ions and anions. The hybrid fluorescent probe (TPPSQ) has been synthesized via cross-linked polymerization between octavinylsilsesquioxane (SQ) and 5,10,15,20-tetrakis-(4-bromophenyl)porphyrin (TPP). Solid-state 29Si and 13C MAS-NMR, FTIR, and energy-dispersive X-ray (EDX) analysis confirmed the successful incorporation of TPP units within the SQ-based network. BET analysis and TGA analysis of the fluorescent nanocomposite revealed that the material possesses excellent thermal stability and a high surface area in the range of 433 m2 g−1, along with bimodal micropores, with a size distribution centered at 0.64 nm and 1.26 nm, and mesopores, with a size distribution centered at 2–3 nm. The incorporation of TPP units into the polymeric network makes the TPPSQ polymer fluorescent (λex = 420 nm, λem = 650 nm) in different media, which is crucial for chemosensing applications. The formation of excimers of TPP units within the polymeric network of TPPSQ plays a pivotal role in selective anion sensing, whereas the interaction capabilities of freebase TPP units with metal ions play a crucial role in cation sensing. Upon the addition of F− ions, TPPSQ showed F−-induced ‘turn-on’ detection due to interactions between the SQ cages and F− ions and the transformation of TPP excimers to monomers. On the other hand, after the addition of Hg2+ ions, TPPSQ showed instant ‘turn-off’ detection because, after the binding of TPP units with Hg2+ ions within the polymeric network, the material undertook a non-radiative relaxation pathway from the excited to the ground state. It is noteworthy that the material is capable of instantly detecting Hg2+ ions in an aqueous medium (DMSO/water ratio of 1 : 7), making it a potential candidate to act as a Hg2+ ion sensor in the real world. This porous nanocomposite (TPPSQ) is capable of adsorbing more than 90% of fluoride ions from solution within 60 min, whereas it can adsorb 76% of CN− ions from solution within 60 min. The nanoporous polymer is also capable of adsorbing 90% of Cu2+ and 88% of Hg2+ from solution within 60 min. The synthesized polymer TPPSQ has shown its excellent efficacy as a reusable fluoride- and Hg2+-ion sensor and as an adsorbent.

Photoswitchable organic materials have shown significant advancement for photonic applications, however, the polynuclear metal clusters conjugated with photoswitching properties are still formidable. Herein, a novel octanuclear Zn(II) nanocage {[Zn8-(Me4Si4O8)2(azopz)8]·4CH2Cl2·MeOH·MeCN} (SD/Zn8) (Hazopz=3,5-dimethyl-4-(phenyldiazenyl)-1H-pyrazole), based on multidentate silsesquioxane and pyrazole modified by photoisomerizable azo group has been designed and synthesized to realize the reversible photoswitching behavior. X-ray crystallographic study reveals that the unique metal core consists of two annular Me4Si4O84− sandwiching a ring of eight Zn atoms where the pyrazole end of azopz− bridges them together. The azopz− ligands diverge above and below the plane defined by eight Zn atoms. Importantly, SD/Zn8 shows quick trans-to-cis transformation upon 365 nm light irradiation, which can be easily changed back by 450 nm light, but slow cis-to-trans reversibility at room temperature as confirmed by UV-Vis and 1H NMR spectroscopies. This process, which presumably regulates the spaces, acts like a pump and is completely repetitive. As such, it can be considered as a molecular pump energized by light. Importantly, the molecule is an energy reservoir where it absorbs the light energy and releases it slowly with time.

International audience; The synthesis of organo-functionalized polyhedral oligomeric silsesquioxanes (POSS, (R-SiO1.5)n, Tn) is an area of significant activity. To date, T14 is the largest such cage synthesized and isolated as a single isomer. Herein, we report an unprecedented, single-isomer styryl-functionalized T18 POSS. Unambiguously identified among nine possible isomers by multinuclear solution NMR (1H, 13C, and 29Si), MALDI-MS, FTIR, and computational studies, this is the largest single-isomer functionalized Tn compound isolated to date. A ring-strain model was developed to correlate the 29Si resonances with the number of 6-, 5-, and/or 4-Si-atom rings that each non-equivalent Si atom is part of. The model successfully predicts the speciation of non-equivalent Si atoms in other families of Tn compounds, demonstrating its general applicability for assigning 29Si resonances to Si atoms in cage silsesquioxanes and providing a useful tool for predicting Si-atom environments

We have successfully synthesized a series of monodispersed chain-like giant molecules with precisely controlled macromolecular composition and sequence based on polyhedral oligomeric silsesquioxane (POSS) nanoparticles using an orthogonal “click” strategy. Their nonspherical supramolecular structures, such as lamellae, double gyroids, and hexagonal packed cylinders, are mainly determined by the composition (namely, the number of incorporated amphiphilic nanoparticles). In addition, by precisely alternating the sequence of arranged nanoparticles in the giant molecules with identical chemical compositions, the domain sizes of their supramolecular structures could be fine-tuned. This is attributed to the macromolecular conformational differences caused by collective hydrogen bonding interactions in each set of sequence isomeric giant molecules. This work has demonstrated multilevel manipulation of supramolecular structures of giant molecules: coarse tuning by composition and fine-tuning by sequence.

Nanostructured solid electrolytes containing ion-conducting domains and rigid nonconducting domains are obtained by block copolymer self-assembly. Here, we report on the synthesis and characteristics of mixtures of a hybrid diblock copolymer with an organic and inorganic block: poly(ethylene oxide)-b-poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (PEO–POSS) and a lithium salt. In the neat state, PEO–POSS exhibits a classical order-to-disorder transition upon heating. Dilute electrolytes exhibit a dramatic reversal; a disorder-to-order transition upon heating is obtained, indicating that the addition of salt fundamentally changes interactions between the organic and inorganic chains. At higher salt concentrations, the electrolytes primarily form a lamellar phase. Coexisting lamellae and cylinders are found at intermediate salt concentrations and high temperatures. The conductivity and shear modulus of PEO–POSS are significantly higher than that of an all-organic block copolymer electrolyte with ...

The hydrogen storage capacity of functionalized Tetrahedral Silsesquioxane (H4Si4O6) cages is obtained using density functional theory (M062X) and second order Moller-Plesset (MP2) method with 6-311++G∗∗ basis set. We labelled Tetrahedral Silsesquioxane (H4Si4O6) as ‘TS’. We replaced four hydrogen in TS one by one with C2HBe or C2HTi group and labelled as TSR1M1, TSR2M2 TSR3M3 and TSR4M4 where RM can be either C2HBe or C2HTi. In TSRM when one hydrogen in a cage is replaced by C2HBe or C2HTi maximum of two and five hydrogen molecules, get adsorbed per Be and Ti atom respectively with respective H2 capacity of 1.61 and 3.42 wt %. H2 uptake capacity of TSRmMm (m = 1, 2, 3 and 4) has increased extensively when all the hydrogen in cage are replaced either C2HBe or C2HTi. TSR4M4 with RM = C2HTi can adsorbs maximum of 20H2 molecules with highest H2 uptake of 7.46 wt % among all the studied complexes. Calculated Gibbs free energy corrected H2 adsorption energies show that adsorption of H2 molecules on all the complexes is thermodynamically favourable. The desorption temperature for the complexes were calculated by using the van't Hoff equation. Calculated interaction energies show that H2 molecules interact strongly with Be atom than Ti atom. The molecular dynamics (MD) simulations have also been performed using atom centered density matrix propagation (ADMP) at ambient conditions. Interaction of hydrogen molecules and the metal atom is confirmed through the density of states (DOS) plot.

We investigated the effects of hydrogen separation using high-temperature anhydrous proton-exchange membrane fuel-cell technology. Various acid-doped para-polybenzimidazole (p-PBI)-chain end-tethered amine-polyhedral oligomeric silsesquioxane (NH2-POSS) membranes were prepared via a unique sol–gel transition method termed as the poly(phosphoric acid) process. The resulting NH2-POSS-capped p-PBI membranes exhibited a higher phosphoric acid-doping level (128–223.5%) and proton conductivity (0.23–0.29 S cm−1 at 160 °C and 0% relative humidity) than the parent p-PBI membrane. The chemical chain end-termination of p-PBI with cage-like NH2-POSS significantly enhanced the electrochemical H2/CO2 and H2/CO separation at 160 °C. The hydrogen separation of the NH2-POSS-capped p-PBI system required a relatively small amount of energy, and the system exhibited a good dynamic response. The favorable interfacial interaction between the NH2-POSS and the p-PBI host, high thermomechanical stability, and good fuel-cell and hydrogen-separation performance at high temperatures up to 160 °C indicate the applicability of the NH2-POSS-capped p-PBI membranes to electrochemical power generation and hydrogen pumps for practical industrial applications in harsh and extreme environments.

Dynamic materials comprising spiropyrans have emerged as one of the most interesting and promising class of stimulus-responsive materials. Spiropyrans are often embedded in polymer matrices; their covalent attachment into porous monolithic silsesquioxane frameworks, however, is virtually unexplored. We demonstrate that a silylated spiropyran derivative can be covalently incorporated into ultralight silsesquioxane-based bulk materials by a two-step co-condensation sol-gel approach without restricting its conformational freedom and thus its stimulus-responsive properties. UV-vis measurements prove the conversion of the colorless closed-ring form of the spiropyran molecule into its highly colored purple isomer or the yellow colored protonated structure thereof. The transformation can be triggered simply by irradiation of the spiropyran-containing silsesquioxane monolith with UV or visible light or by the pH value of the chemical environment. A strong dependence of the surface polarity and water wettability on the prevalent isomer was observed. The contact angle of a water droplet on the monolithic surface can be altered from 146 to 100° by irradiation of the monolith with UV light for 3 min. Additionally, the prepared materials possess high specific surface areas, low bulk densities, and porosities of up to 84%.

A8-type eight-arm star-shaped poly(ε-caprolactone) (PCL) polymers with polyhedral oligomeric silsesquioxane (POSS) (SP) core having different molecular weight with different chain lengths (n=10, 20, 30, and 50 repeating units) were synthesized via arm-first approach by combination of ring-opening polymerization (ROP) and “click” chemistry reactions. The obtained polymers were then melt-blended with neat poly(lactic acid) (PLA) to improve some of the properties like toughness of PLA. These blends were prepared depending on the blend ratio (95/5 and 80/20 wt%) via utilizing laboratory scale twin-screw mini extruder to examine morphological, thermal and mechanical properties of PLA/SP composite as a function of SP and blending ratio. In addition, the PLA/SP composites containing a blend ratio of 90/10 wt% which were prepared in the previous study was used to compare with other composite having different blend ratio. The incorporation of SP polymers improved some of the mechanical properties of PLA. It was verified that SP20 (n=20) is the most proper SP-type for enhancing the mechanical behavior of PLA at a blending ratio of 90/10. Also, 1,4-phenylene diisocyanate (PDI) which was used as a commercial compatibilizer was incorporated to blends at fixed amount (%1). It is concluded that the incorporation of SP polymers into PLA matrix decreased the tensile modulus with increasing blending ratio and increased the elongation at break values in the presence of PDI.

We have studied synthesis, activity, epoxide selectivity, H2O2 efficiency, and recyclability of new robust heterogeneous alkene epoxidation catalysts of grafted tripodal (phenoxy) Ti-polyhedral oligomeric silsesquioxane (Ti-POSS) complexes in hyperbranched poly(siloxysilane) matrix. Crosslinked hyperbranched (CHB) poly(siloxysilane)-grafted [Ti(OC6H4CN-p){(HSiMe2(CH2)3)-(i-C4H9)6Si7O12}] (5) and CHB-poly(siloxysilane)-grafted [Ti(OC6H5){(HSiMe2(CH2)3)(i-C4H9)6Si7O12}] (6) have demonstrated high activity, epoxide selectivity (≥99%) and H2O2 efficiency (≥98%) in cyclohexene and 1-octene epoxidation with aqueous H2O2 higher than titanosilicate catalysts such as TS-1 and Ti-β, due to high Lewis acidity of the Ti-center and to the use of CHB-poly(siloxysilane) matrix. The catalysts are readily recyclable with retained activity.

In the present research, the synthesis, spectroscopic characterization, and structural investigations of a unique ZnII complex of imine-functionalized polyhedral oligomeric silsesquioxane (POSS) is designed, and hereby described, as a catalyst for the synthesis of cyclic carbonates from epoxides and CO2. The uncommon features of the designed catalytic system is the elimination of the need for a high pressure of CO2 and the significant shortening of reaction times commonly associated with such difficult transformations like that of styrene oxide to styrene carbonate. Our studies have shown that imine-POSS is able to chelate metal ions like ZnII to form a unique coordination complex. The silsesquioxane core and the hindrance of the side arms (their steric effect) influence the construction process of the homoleptic Zn4@POSS-1 complex. The compound was characterized in solution by NMR (1H, 13C, 29Si), ESI-MS, UV/Vis spectroscopy and in the solid state by thermogravimetric/differential thermal analysis (TG-DTA), elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), cross-polarization magic angle spinning (CP MAS) NMR (13C, 29Si) spectroscopy, and X-ray crystallography.

In the present work, we prepared the MWCNT-L-POSS from the grafting reaction between octa (propylglycidyl ether) polyhedral oligomeric silsesquioxane (POSS) and multi-wall carbon nanotubes (MWCNT)....

Here, transparent films were prepared from regenerated cellulose. Microcrystalline cellulose was solubilized in N,N-dimethylacetamide with lithium chloride. Exchange of organic solvent for water re...

A total of 1/2/4/6-armed molecular architectured polyhedral oligomeric silsesquioxane (POSS) fluoropolymers were synthesized via atom transfer radical polymerization (ATRP) by linear (L), dicephalus (D), four-arm (T), and six-arm (S) initiators initiating same content of methyl methacrylate (MMA), methacrylate POSS (MA-POSS), and dodecafluoroheptyl methacrylate (DFHM). The obtained L/D/T/S-(PMMA-b-PMAPOSS-b-PDFHM)1/2/4/6 had increased molecular weight with arm increase. Driven by the stereo-hindrance and curvature effects of segments in tetrahydrofuran (THF), they assembled into the decreased spherical core-shell micelles (250–100 nm) with arm increase as PMA-POSS/PDFHM core and PMMA shell. Because of easy surface migration of fluorine-containing groups in small micelles, the casted film by S-(PMMA-b-PMAPOSS-b-PDFHM)6 performed the fluorine-rich (46.44%) and rough (5.41 nm) surface, and therefore with the hydrophobic (112°) and low water adsorption surface (1522 ng/cm2). Also, POSS-fluoropolymers obtained the enhanced thermostability with arm increase. It is believed that this research will provide a bright view for design and application of POSS-fluoropolymers.

Nanoadditives are promising materials for long-envisioned next-generation lubricants to achieve excellent tribological performance and thermal stability. Here, an instigative and novel approach has been scrutinized to facilely prepare the nanolubricant additive. For this purpose, three synthetic strategies were designed for i) preparation of uniform-sized poly(methyl silsesquioxane) (PMSQ) nanoparticles, ii) hydrosilylation of the long carbon chain of ethyl 10-undecenoate and iii) modification of PMSQ nanoparticles with hydrosilylation product through a condensation reaction, in order to obtain long-carbon-chain grafted nanohybrids. The morphology, composition, and properties of these nanohybrids were confirmed by 1H-NMR, FTIR, SEM, EDS, and TGA. The effects of different concentrations of unmodified and modified PMSQ nanoparticles on the tribological properties of silicone oil were discussed. In the comparison of unmodified PMSQ nanoparticles, the modified one performs very well to reduce the coefficient of friction and wear scar diameter at low concentration. The TGA results revealed the extraordinary thermal stability of these particles, as their weight loss was only 19% at 800 °C which is remarkably higher than other solid lubricant additives. In this research, we tried to fill the deficiency of thermally stable material in the field of heavy machinery and industry. In addition, the environment-friendly (fluorine-free), superhydrophobic and self-cleaning surface effect of modified PMSQ nanoparticles was also observed. These silsesquioxane-based nanohybrids having synergistic effects, advantageous scientific values, and promising application prospects are expected to be more useful with other longer carbon chains.

Acrylic acid-modified polyhedral oligomeric silsesquioxane (AC-POSS) was synthesized by the reaction between the amine groups in polyhedral oligomeric silsesquioxane (POSS) and acrylic acid, which could dissolve in water and can be easily purified. Free-radical copolymerization was applied to synthesize azobenzene liquid crystalline polymer silsesquioxane (LCP-POSS) with different proportions of AC-POSS and liquid crystalline monomers. The trans-isomers of azobenzene moieties in LCP-POSS were gradually transformed to cis-isomers with increasing ultraviolet irradiation time. The photoisomerization reaction of liquid crystalline polymer (LCP) and LCP-POSS showed the first-order dynamic reaction. Compared with the LCP, the photoisomerization rate constant of LCP-POSS was decreased due to the space steric hindrance of the POSS as a rigid segment. The phase transition temperature of liquid crystalline in LCP-POSS increased with increasing POSS content, and the liquid crystalline texture in LCP-POSS became smaller under the polarized light. With further increasing the POSS content (>50 wt%) in LCP-POSS, the ordered structure of the liquid crystalline phase was gradually affected, resulting in one-way liquid crystal (LC) phase behavior. The synthesized LCP-POSS has LC properties, light-responsive properties, and thermal stability. When the POSS is introduced into the LC material, the phase state of the LC material will become more abundant and the LC phase will become more stable. The significance of this study is to develop and extend its applications as stimuli-responsive materials and devices.