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.

Metallodendrimers Unveiled: Investigating the Formation and Features of Double-Decker Silsesquioxane-Based Silylferrocene Dendrimers.

Dendrimers exhibiting reversible redox properties have attracted extensive attention for their potential as electron transfer mediators, catalysts, and molecular sensors. In this study, we introduce intriguing G1 and G2 dendrimers featuring double-decker silsesquioxane cores and silylferrocene moieties. Through a carefully orchestrated sequence of condensation, reduction, and hydrosilylation reactions, these compounds were synthesized and comprehensively characterized spectroscopically and spectrometrically. Our investigation also encompassed the examination of their properties, including thermal stability, solubility in common organic solvents, and electrochemical behavior. We determined that these dendrimers possess the capability to form monolayers on platinum electrodes, which we conclusively demonstrated through the probing of cyclic voltammetry, electrochemical impedance spectroscopy, and scanning electron microscopy imaging. Notably, this study marks the first-ever example of modifying double-decker silsesquioxane cores with ferrocene groups while simultaneously representing one of the scarce instances of dendrimers exhibiting an open double-decker silsesquioxane core.

Slick Synthetic Approach to Various Fluoroalkyl Silsesquioxanes-Assessment of their Dielectric Properties.

We present a smart and efficient methodology for the synthesis of a variety of fluorinated silsesquioxanes (SQs) with diverse Si-O-Si core architecture. The protocol is based on an easy-to-handle and selective hydrosilylation reaction. An investigation on the placement of the reactive Si-HC=CH2 vs. Si-H in the silsesquioxane, as well as silane vs. olefin structure, respectively, on the progress and selectivity of the hydrosilylation process, was studied. Two alternative synthetic pathways for obtaining a variety of fluorine-functionalized silsesquioxanes were developed. As a result, a series of mono- and octa- T8 SQs, tri- 'open-cage' T7 SQs, in addition to di- and tetrafunctionalized double-decker silsesquioxane (DDSQ) derivatives, were obtained selectively with high yields. All products were characterized by spectroscopic (NMR, FTIR) techniques. Selected samples were subjected to the measurements revealing their dielectric permittivity in a wide range of temperatures (from -100 °C to 100 °C) and electric field frequencies (100-106 Hz).

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 ß-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.

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.

Polysiloxanes Grafted with Mono(alkenyl)Silsesquioxanes-Particular Concept for Their Connection.

Herein, a facile and efficient synthetic route to unique hybrid materials containing polysiloxanes and mono(alkyl)silsesquioxanes as their pendant modifiers (T8@PS) was demonstrated. The idea of this work was to apply the hydrosilylation reaction as a tool for the efficient and selective attachment of mono(alkenyl)substituted silsesquioxanes (differing in the alkenyl chain length, from -vinyl to -dec-9-enyl and types of inert groups iBu, Ph at the inorganic core) onto two polysiloxanes containing various amount of Si-H units. The synthetic protocol, determined and confirmed by FT-IR in situ and NMR analyses, was optimized to ensure complete Si-H consumption along with the avoidance of side-products. A series of 20 new compounds with high yields and complete ß-addition selectivity was obtained and characterized by spectroscopic methods.

Formation of Bifunctional Octasilsesquioxanes via Silylative Coupling and Cross-Metathesis Reaction.

Bifunctional silsesquioxanes create an attractive group of compounds with a wide range of potential applications, and recently they have gained much interest. They are known to be obtained mainly via hydrosilylation, but we disclose novel synthetic protocols based on different but complementary reactions, i.e., cross-metathesis (CM) and silylative coupling (SC). A series of cubic T8 type silsesquioxane derivatives with a broad scope of styryl substituents were synthesized in a one-pot procedure and characterized by spectroscopic and spectrometric methods. All of the new compounds can be obtained in a one-pot manner, which has an attractive impact on the synthetic procedure, as it is economic in terms of the isolation of intermediate products. Additionally, the methodology disclosed here enables the (E)-stereoselective introduction of styrenes derivative to the cubic T8 type core. The presented compounds can be interesting precursors for a further functionalization that may significantly increase the possibility of their application in the design and synthesis of new functional materials.

Preparation of Tri(alkenyl)functional Open-Cage Silsesquioxanes as Specific Polymer Modifiers.

The scientific reports on polyhedral oligomeric silsesquioxanes are mostly focused on the formation of completely condensed T8 cubic type structures and recently so-called double-decker derivatives. Herein, we report on efficient synthetic routes leading to trifunctionalized, open-cage silsesquioxanes with alkenyl groups of varying chain lengths from -vinyl to -dec-9-enyl and two types of inert groups (iBu, Ph) at the silsesquioxane core. The presented methodology was focused on hydrolytic condensation reaction and it enabled obtaining titled compounds with high yields and purity. A parallel synthetic methodology that was based on the hydrosilylation reaction was also studied. Additionally, a thorough characterization of the obtained compounds was performed, also in terms of their thermal stability, melting and crystallization temperatures (TGA and DSC) in order to show the changes in the abovementioned parameters dependent on the type of reactive as well as inert groups at Si-O-Si core. The presence of unsaturated alkenyl groups has a profound impact on the application potential of these systems, i.e., as modifiers or comonomers for copolymerization reaction.

Synthetic Routes to Silsesquioxane-Based Systems as Photoactive Materials and Their Precursors.

Over the past two decades, organic optoelectronic materials have been considered very promising. The attractiveness of this group of compounds, regardless of their undisputable application potential, lies in the possibility of their use in the construction of organic⁻inorganic hybrid materials. This class of frameworks also considers nanostructural polyhedral oligomeric silsesquioxanes (POSSs) with "organic coronae" and precisely defined organic architectures between dispersed rigid silica cores. A significant number of papers on the design and development of POSS-based organic optoelectronic as well as photoluminescent (PL) materials have been published recently. In view of the scientific literature abounding with numerous examples of their application (i.e., as OLEDs), the aim of this review is to present efficient synthetic pathways leading to the formation of nanocomposite materials based on silsesquioxane systems that contain organic chromophores of complex nature. A summary of stoichiometric and predominantly catalytic methods for these silsesquioxane-based systems to be applied in the construction of photoactive materials or their precursors is given.

Anchor Effect in Polymerization Kinetics: Case of Monofunctionalized POSS.

The effect of the anchoring group on the detailed polymerization kinetics was investigated using monomethacryloxy-heptaisobutyl POSS (1M-POSS). This compound was copolymerized with lauryl methacrylate (LM) as the base monomer, at various molar ratios. The process was initiated photochemically. The polymerization kinetics were followed by photo-DSC and photorheology while the polymers were characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). For comparison, a methacrylate containing the branched siloxy-silane group (TSM) was also studied. It was found that the modifiers with a bulky substituent have a dual effect on the termination process: (i) At low concentrations, they increase the molecular mobility by increasing the free volume fraction, which leads to an acceleration of the termination and slows the polymerization; while (ii) at higher concentrations, they retard molecular motions due to the "anchor effect" that suppresses the termination, leading to acceleration of the polymerization. The anchor effect can also be considered from a different point of view: The possibility of anchoring a monomer with a long substituent (LM) around the POSS cage, which can further enhance propagation. These conclusions were derived based on kinetic results, determination of polymerization rate coefficients, and copolymer analysis.

Synthesis of (E)-1,4-disilsesquioxylsubstituted but-1-en-3-ynes via platinum-catalyzed dimerization of ethynylsiloxysilsesquioxanes.

A new platinum complex bearing bulky N-heterocyclic carbene ligand of the general formula [Pt(IPr*Ph)(dvtms)] (where IPr*Ph = 1,3-bis{2,4,6-tris(diphenylmethyl)phenyl}imidazol-2-ylidene, dvtms = divinyltetramethyldisiloxane) exhibits a high catalytic activity towards E-selective dimerization of ethynyl substituted siloxysilsesquioxanes. This process leads to a novel class of functionalized silsesquioxane derivatives, resembling their dumbbell-shaped silsesquioxane analogues.

N-Heterocyclic carbene-based ruthenium-hydride catalysts for the synthesis of unsymmetrically functionalized double-decker silsesquioxanes.

Ruthenium-N-heterocyclic carbene complexes with the generic formula [RuHCl(CO)(NHC)(PCy3)] exhibit a high catalytic activity toward the (E)-selective silylative coupling of divinyl-substituted double-decker silsesquioxanes with two distinctly substituted styrenes. This process leads to a novel class of unsymmetrically functionalized silsesquioxane derivatives.

Multi-Alkenylsilsesquioxanes as Comonomers and Active Species Modifiers of Metallocene Catalyst in Copolymerization with Ethylene.

The copolymers of ethylene (E) with open-caged iso-butyl-substituted tri-alkenyl-silsesquioxanes (POSS-6-3 and POSS-10-3) and phenyl-substituted tetra-alkenyl-silsesquioxane (POSS-10-4) were synthesized by copolymerization over the ansa-metallocene catalyst. The influence of the kind of silsesquioxane and of the copolymerization conditions on the reaction performance and on the properties of the copolymers was studied. In the case of copolymerization of E/POSS-6-3, the positive comonomer effect was observed, which was associated with the influence of POSS-6-3 on transformation of the bimetallic ion pair to the active catalytic species. Functionality of silsesquioxanes and polymerization parameters affected the polyhedral oligomeric silsesquioxanes (POSS) contents in the copolymers which varied in the range of 1.33⁻7.43 wt %. Tri-alkenyl-silsesquioxanes were incorporated into the polymer chain as pendant groups while the tetra-alkenyl-silsesquioxane derivative could act as a cross-linking agent which was proved by the changes in the contents of unsaturated end groups, by the glass transition temperature values, and by the gel contents (up to 81.3% for E/POSS-10-4). Incorporation of multi-alkenyl-POSS into the polymer chain affected also the melting and crystallization behaviors.

Manganese-Catalyzed Sustainable Synthesis of Pyrroles from Alcohols and Amino Alcohols.

The development of reactions that convert alcohols into important chemical compounds saves our fossil carbon resources as alcohols can be obtained from indigestible biomass such as lignocellulose. The conservation of our rare noble metals is of similar importance, and their replacement by abundantly available transition metals, such as Mn, Fe, or Co (base or nonprecious metals), in key technologies such as catalysis is a promising option. Herein, we report on the first base-metal-catalyzed synthesis of pyrroles from alcohols and amino alcohols. The most efficient catalysts are Mn complexes stabilized by PN5 P ligands whereas related Fe and Co complexes are inactive. The reaction proceeds under mild conditions at catalyst loadings as low as 0.5 mol %, and has a broad scope and attractive functional-group tolerance. These findings may inspire others to use Mn catalysts to replace Ir or Ru complexes in challenging dehydrogenation reactions.

Iridium complex catalyzed germylative coupling reaction between alkynes and iodogermanes--a new route to alkynylgermanium and alkynylgermasilicon compounds.

The new reaction of terminal alkynes with iodogermanes proceeding in the presence of an Ir(I)-complex [{Ir(µ-Cl)(CO)2}2] (I) and NEt((i)Pr)2, as a hydrogen iodide acceptor, leads to the formation of functionalized alkynylgermanes. This reaction occurs via direct activation of the C(sp)-H bond in the starting alkyne. Detailed stoichiometric experiments using [Ir(cod)(CCPh)(PCy3)] (IVa) and iodogermane were performed and resulted in a proposal of a reasonable mechanism for the germylative coupling reaction between alkynes and iodogermanes.

New mono- and diethynylsiloxysilsesquioxanes--efficient procedures for their synthesis.

Ethynyl-substituted siloxysilsesquioxanes are promising building blocks for a wide range of substances based on a POSS/DDSQ core, especially for (oligo-)polymer syntheses and modifications (the formation of hybrid materials with interesting photophysical and mechanical properties). In this study, we report on a series of new mono- and diethynylsiloxysilsesquioxanes formed via an efficient and highly selective one-pot process from silsesquioxanes with reactive Si-OH groups based on sequential condensation, hydrolysis, chlorination and substitution reactions. All newly synthesized compounds were isolated and characterized by spectroscopic methods.

Silylative coupling versus metathesis--efficient methods for the synthesis of difunctionalized double-decker silsesquioxane derivatives.

A series of functionalized dialkenylsilsesquioxanes were obtained by efficient and highly stereoselective silylative coupling and cross-metathesis of divinylsubstituted double-decker silsesquioxanes (DDSQ-2SiVi) with substituted styrenes and other olefins. Both reactions proceed highly stereoselectively and lead to nearly quantitative formation of E isomers. The optimized reaction conditions for styrene were adopted for successful silylative coupling polycondensation of DDSQ-2SiVi with 1,4-divinylbenzene yielding stereoregular cooligomer containing double-decker (silsesquioxyl-silylene)-vinylene-phenylene units.