Double-decker Silsesquioxanes Research Articles

Thermal and mechanical properties of PLA/ENR thermoplastic vulcanizates compatibilized with tetrafunctional double-decker silsesquioxanes

The influence of the addition of tetrafunctional double-decker silsesquioxanes (DDSQ-ether-4OH) on the compatibility, thermal and mechanical properties of polylactide and epoxidized natural rubber (PLA/ENR) vulcanizates was investigated. The apparent cross-linking density and thermal stability of PLA/ENR vulcanizates were also determined. The FTIR analysis confirmed the compatibilizing effect of DDSQ-ether-4OH and the formation of the PLA-g-ENR copolymer. A strong effect of ENR content and DDSQ-ether-4OH addition on the thermal and mechanical properties of the obtained vulcanizates was demonstrated.

Exploring Polyol-Functionalized Dendrimers with Silsesquioxane Cores.

Silsesquioxane dendrimers offer versatile structural potential, prompting our innovative synthesis of G1 and G2 polyol dendritic systems with diverse silsesquioxane cores, ranging from mono-T8 to difunctional and tetrafunctional double-decker silsesquioxanes. Through a strategic combination of hydrosilylation and O-silylation reactions, we have formed an extensive compound library. A major focus was directed toward investigating the reaction conditions of G1.5 dendrimers, as well as evaluating the stability and reactivity of the novel -O-Me2Si-H group. Notably, we unveiled solubility trends of these synthesized dendritic systems in basic organic solvents, offering vital information for potential applications. Our work advances dendrimer research by unraveling intricate synthesis, reactivity, and properties. We contribute to the broader understanding of these organic-inorganic complex interactions and envisage diverse applications in multiple domains.

Unprecedented Route to Amide-Functionalized Double-Decker Silsesquioxanes Using Carboxylic Acid Derivatives and a Hydrochloride Salt of Aminopropyl-DDSQ.

An easy, efficient, and scalable synthetic procedure is described to obtain novel amide-functionalized double-decker silsesquioxanes (DDSQs). The use of mild conditions of deprotection of the BOC group, which does not result to the cleavage of the cage-like silsesquioxane structure, is reported. This method leads to the so far undescribed hydrochloride salt of aminoalkyl-DDSQ. Interestingly, the cis/trans-isomerization of DDSQ molecules was observed during the reaction. The resulting compounds are characterized using multinuclear NMR (1H, 13C, and 29Si), MALDI-TOF, FT-IR, and elemental analysis. Moreover, crystal structures are reported for three trans DDSQs. The chloride salt of aminoalkyl derivative, obtained in one of the steps of the synthetic pathway, shows an intriguing structure of the crystal lattice in which large channels are present, caused by ionic interactions in the lattice. The described approach opens the way to synthesizing new DDSQ derivatives and materials using BOC-blocked amines. We believe our findings would advance investigations about new materials based on little known organic-inorganic DDSQ-based hybrids.

Novel hybrid composites based on double-decker silsesquioxanes functionalized by methacrylate derivatives and polyvinyl alcohol as potential materials utilized in biomedical applications

The use of diverse biomaterials for regenerative medicine is constantly evolving. Therefore, looking for easy-to-scale-up materials in terms of preparation, less complex composition, and featuring structural and chemical stability seems justified. In this work, we report the preparation of double-decker silsesquioxane-based (DDSQ-based) composites, which, according to our best knowledge, have never been used as biomaterials. A family of methacrylate-substituted DDSQs was obtained starting from the previously reported hydroxyalkyl double-decker silsesquioxanes. In the resulting hybrids, methacrylate groups are attached to each other's lateral silicon atoms of DDSQ in trans positions, providing an excellent geometry for forming thin layers. In contrast to pure organic methacrylates, the covalent bonding of methacrylate derivatives to inorganic silsesquioxane core improves mechanics, cell adhesion, and migration properties. Furthermore, to increase the hydrophilicity of the resulting DDSQ-based hybrids, polyvinyl alcohol (PVA) was added. The entire system forms an easy-to-obtain two-component (DDSQ-PVA) composite, which was subjected without any upgrading additives to biological tests later in the research. The resulting biomaterials fulfill the requirements for potential medical applications. Human fibroblasts growing on prepared hybrid composites are characterized by proper spindle-shaped morphology, proliferation, and activation status similar to control conditions (cells cultured on PVA), as well as increased adhesion and migration abilities. The obtained results suggest that the prepared biomaterials may be used in regenerative medicine in the future.

Tricky but repeatable synthetic approach to branched, multifunctional silsesquioxane dendrimer derivatives

The efficient one-pot procedure based on a sequence of hydrosilylation and reduction reactions was applied to obtain carbosilane dendrimers with different silsesquioxane (SQ) cores,i.e.from mono-T8SQ, octa-T8SQ to di- and tetrafunctional double-decker silsesquioxanes.

Distinct insight into the use of difunctional double-decker silsesquioxanes as building blocks for alternating A–B type macromolecular frameworks

A distinct look at known, hydrosilylation reactions used for the formation of DDSQ-based linear A–B alternating macromolecular systems with DPn > 1000 is presented. Selected physicochemical properties of obtained hybrid co-polymers were determined.

Self-Healing Silsesquioxane-Based Materials

This review is devoted to self-healing materials (SHM) containing polyhedral oligomeric silsesquioxanes (POSS) as building blocks. The synthetic approach can vary depending on the role POSS are expected to play in a given system. POSS (especially double-decker silsesquioxanes) can be grafted in side chains of a polymer backbone or used as segments of the main chain. Appropriate functionalization allows the formation of dynamic bonds with POSS molecules and makes them an active component of SHM, both as crosslinking agents and as factors that enhance the dynamics of macromolecules in the polymer matrix. The latter effect can be achieved by reversible release of bulky POSS cages or by the formation of separated inclusions in the polymer matrix through hydrophobic interactions and POSS aggregation. The unique properties of POSS-based self-healing systems make them interesting and versatile materials for various applications (e.g., repairable coatings, sealants, sensors, soft materials for tissue engineering, drug delivery, and wound healing).

High thermally stable polysiloxanes cross-linked with di(alkenyl)functionalized DDSQs exhibiting swelling abilities

A series of unique organic–inorganic hybrid materials varied in the construction of the applied polysiloxanes and di(alkenyl)functionalized double-decker silsesquioxanes was designed, synthesized and fully characterized by spectroscopic methods. The presented synthetic strategy based on hydrosilylation reaction conditions was optimized to ensure complete Si-H consumption along with the avoidance of side-products enabling the formation of materials with high conversion. The obtained results revealed the influence of the type and content of DDSQ in cross-linked polymers structures on their thermal and swelling properties which has not been reported so far. Our studies can lead to the preparation of specific materials with tailored properties.

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

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.

Vinyl- and chloromethyl-substituted mono-T8 and double-decker silsesquioxanes as specific cores to low generation dendritic systems.

We report the series of G1 and G1.5 dendritic systems with mono-T8 SQs and DDSQ as specific types of dendron and dendrimer cores, respectively. The trivinyl- and tri(chloromethyl)-derivatives were obtained via hydrolytic condensation followed by the hydrosilylation reaction, optimized to yield selectively β-products. Their structures were confirmed by spectroscopic and XRD analyses. It is the first example of double-decker SQs used as cores for the construction of a low generation of dendrimer featuring specific dumbbell frameworks expanding in two or four directions.

Hydroxyalkyl-substituted double-decker silsesquioxanes: effective separation ofcisandtransisomers

A procedure to sequentially crystallize the two isomers of hydroxyalkyl-substituted double-decker silsesquioxanes from one another, which may result in the preparation of new materials and polymers with well-defined properties, is reported.

Unexpected and frustrating transformations of double-decker silsesquioxanes

This paper outlines an unexpected type of intramolecular transformation of DDSQ during hydrolytic condensation and surprising catalytic reactivity in silylative coupling.

Double-Decker Silsesquioxanes Self-Assembled in One-Dimensional Coordination Polymeric Nanofibers with Emission Properties.

The urgent needs for photoactive materials in industry drive fast evolution of synthetic procedures in many branches of chemistry, including the chemistry of silsesquioxanes. Here, we disclose an effective protocol for the synthesis of novel double-decker silsesquioxanes decorated with two (styrylethynylphenyl)terpyridine moieties (DDSQ_Ta-b). The synthesis strategy involves a series of silylative and Sonogashira coupling reactions and is reported for the first time. DDSQ_Ta-b were employed as nanocage ligands to promote self-assembly in the presence of transition metals (TM), i.e., Zn2+, Fe2+, and Eu3+ ions, to form one-dimensional (1D) coordination polymeric nanofibers. Additionally, ultraviolet-promoted and reversible E–Z isomerization of the C=C bond within the ligand structures may be exploited to tune their emission properties. These findings render such complexes promising candidates for applications in materials chemistry. This is the first example of 1D coordination polymers bearing DDSQ-based nodes with TM ions.

Synthesis of Silsesquioxanes with Substituted Triazole Ring Functionalities and Their Coordination Ability.

A synthesis of a series of mono-T8 and difunctionalized double-decker silsesquioxanes bearing substituted triazole ring(s) has been reported within this work. The catalytic protocol for their formation is based on the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) process. Diverse alkynes were in the scope of our interest—i.e., aryl, hetaryl, alkyl, silyl, or germyl—and the latter was shown to be the first example of terminal germane alkyne which is reactive in the applied process’ conditions. From the pallet of 15 compounds, three of them with pyridine-triazole and thiophenyl-triazole moiety attached to T8 or DDSQ core were verified in terms of their coordinating properties towards selected transition metals, i.e., Pd(II), Pt(II), and Rh(I). The studies resulted in the formation of four SQs based coordination compounds that were obtained in high yields up to 93% and their thorough spectroscopic characterization is presented. To our knowledge, this is the first example of the DDSQ-based molecular complex possessing bidentate pyridine-triazole ligand binding two Pd(II) ions.

Assembly of discrete and oligomeric structures of organotin double-decker silsesquioxanes: inherent stability studies

Discrete and oligomeric organotin DDSQs have been synthesized and characterized, both experimentally and through computational study. The stability of these compounds remains intrigued with the organization of their structure in the crystal lattice.

Organic–Inorganic Polycyclooctadienes with Double-Decker Silsesquioxanes in the Main Chains: Synthesis, Self-Healing, and Shape Memory Properties Regulated with Quadruple Hydrogen Bonds

Double-decker silsesquioxane (DDSQ) cages were introduced into the main chains of polycyclooctadiene via a ring-opening metathesis polymerization (ROMP) approach. Toward this end, a macromolecular ...

Poly(hydroxyl urethane)s with Double Decker Silsesquioxanes in the Main Chains: Synthesis, Shape Recovery, and Reprocessing Properties

3,13-Di(cyclic carbonate) double decker silsesquioxane, a new difunctional polyhedral oligomeric silsesquioxane (POSS), was successfully synthesized. By using this POSS macromer, the organic–inorga...

Synthesis of Double-Decker Silsesquioxanes from Substituted Difluorosilane

A novel synthetic method for the construction of a double-decker silsesquioxane from fluorosilanes was developed. Phenyl-substituted double-decker silsesquioxane was prepared under mild conditions by coupling difluorodiphenylsilane and a tetrasiloxanolate precursor. A similar reaction was performed using difluorovinylsilane, and a divinyl double-decker silsesquioxane was obtained. The one-step reaction of a functional difluorosilane containing an aminopropyl group afforded a novel double-decker silsesquioxane with two amino groups complexed with BF3, which can react with carboxylic acid anhydrides to afford an amide product. This synthetic method using difluorosilane is tolerant of a wide range of functional groups and is applicable to the synthesis of polycyclic silsesquioxanes bearing amino groups, which are difficult to directly obtain from dichlorosilane.

Separation of asymmetrically capped double-decker silsesquioxanes mixtures

A synthetic path to asymmetric side-capped double-decker shaped silsesquioxanes (DDSQ) and subsequent isolation is described. By strategically using a combination of dichloro and trichlorosilane capping agents, a resultant product with mixed silanol functionalities was obtained. The use of preparatory liquid chromatography (LC) cleanly separated DDSQ compound with asymmetric functionality, and HPLC provided a quantitative technique to analyze mixture ratios. These mixture ratios did not follow the expected statistical trend due to the steric effects on the rate of capping. As a consequence, a decreased amount of the desired asymmetric DDSQ was observed in some cases. This was overcome by varying the ratio of capping agents. Overall, this work demonstrates access to asymmetric DDSQ cages is feasible, and LC is an effective separation technique.

Organic–inorganic polyurethanes with double decker silsesquioxanes in the main chains: Morphologies, surface hydrophobicity, and shape memory properties

ABSTRACTIn this contribution, we reported an investigation of the morphologies, surface hydrophobicity, and shape memory properties of the organic–inorganic polyurethanes with double decker silsesquioxane (DDSQ) in the main chains. It was found that the organic–inorganic polyurethanes were microphase‐separated and that the POSS cages in the main chains were self‐organized into the spherical microdomains with the size of 10–50 nm in diameter. The introduction of POSS cages into the main chains resulted in the enhancement of glass transition temperatures (Tg's). In the meantime, the surface dewettability of the materials was significantly enhanced. X‐ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) indicates the improvement of the surface hydrophobicity resulted from the enrichment of POSS at the surfaces of the polyurethanes. The mechanical analyses, such as dynamic mechanical analysis (DMA) and creep‐recovery analysis (CRA), indicate that the POSS microdomains dispersed in the polyurethanes behaved as the physical crosslinking sites and promoted the formation of the crosslinked networks. Owing to the introduction of DDSQ into the main chains, the organic–inorganic polyurethanes significantly displayed shape memory properties, in marked contrast to the unmodified and linear polyurethane. The shape memory behavior has been addressed on the formation of the strong physically crosslinked networks in the organic–inorganic polyurethanes. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 893–906