Preparation and Characterization of Polyhedral Oligosilsesquioxanes

Cordes, David B.; Lickiss, Paul D.

doi:10.1007/978-90-481-3787-9_2

Cited by 24 publications

(16 citation statements)

References 441 publications

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“…Polyhedral oligomeric silsesquioxanes (POSSs), compounds with a rigid inorganic core composed of a Si–O–Si bond framework surrounded by organic groups, have found increasing applications in various fields including polymers, sensors, catalysis, host–guest complexes, organic light-emitting diodes, and porous materials ,. While a wide array of mono- or octafunctional derivatives of T 8 silsesquioxanes have been described, the double-decker siloxanes (DDSQs) bearing reactive substituents have been less studied (Scheme ). Both open M 4 T 8 (DDSQ-4OSi, Scheme a) and closed D 2 T 8 (DDSQ-2OSi, Scheme b) frameworks have been applied in various areas of chemistry such as coordination chemistry, optics, or hybrid polymer nanocomposites. , To include DDSQ architectures in more complex systems (for example, coordination complexes, electronic or optic devices, hybrid polymers, and so on), the prerequisite consists of decorating the M 4 T 8 and D 2 T 8 DDSQ architectures with reactive groups (Scheme a and b, respectively).…”

Section: Introductionmentioning

confidence: 99%

“…It is worth noting that the number of reactive groups grafted on the inorganic core appears as decisive to define the further properties of the POSSs, as illustrated by the strongly different behaviors of mono- or polysubstituted POSS in a given application. For example, T 8 bearing one boron-dipyrromethene fluorophore displayed significantly better lasing efficiency and photostability than their octafunctionalized counterparts, while multivalency is a strong asset for catalytic or biological applications . The fine-tuning of external functional groups on the POSS thus constitutes a strategic challenge.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Tetrachloro, Tetraiodo, and Tetraazido Double-Decker Siloxanes

et al. 2020

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A convenient and scalable (gram-scale) route to unprecedented T8D2-DDSQs bearing four chloro-(3b) or four azido (5b) groups is reported. Both compounds were characterized and proved to undergo successfully nucleophilic substitution for 3b (with iodide or azide) and coppercatalyzed azide-alkyne [3+2] cycloaddition for 5b. All these transformations occurred under mild conditions and the corresponding DDSQs were prepared in very high yields. Beyond the enhanced multivalency as compared to the previously described di-substituted D2T8 structures, the reported tetra-functional DDSQs are formed as a single isomer and readily isolated in very high yields.Moreover, the tetra-azido DDSQ 5b constitutes a multipurpose nano-building block for the further preparation of new inorganic-organic hybrid materials where the covalent incorporation of a DDSQ moiety brings valuable properties.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis of Tetrachloro, Tetraiodo, and Tetraazido Double-Decker Siloxanes

et al. 2020

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“…Silsesquioxanes, organosilicon compounds with the empirical formulas RSiO 3/2 (R = H, alkyl, aryl), have been extensively studied due to their interesting properties such as thermal stability, low dielectric constant, and water repellency . Several types of well-defined silsesquioxanes have been reported and include partially condensed, cages (e.g. T 8 , T 10 , and T 12 ), or ladder structures (so-called “laddersiloxanes”).…”

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confidence: 99%

Synthesis and Characterization of Functionalizable Silsesquioxanes with Ladder-type Structures

et al. 2019

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HAL is a multi-disciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L'archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d'enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.

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“…MJPs can be prepared as individual giant molecules using molecular nanoparticles (MNPs) , or so-called “nano-atoms”, as the building blocks, which are shape- and volume-persistent nanoscale objects with precisely defined molecular symmetry and surface functionalities. The explored library of MNPs includes derivatives of polyhedral oligomeric silsesquioxanes (POSS), − [60]fullerene (C 60 ), polyoxometalates (POMs), − and folded protein domains. , Solution self-assembly behaviors of MJPs are determined by the relative solubility of their different components in a specific solvent. When selective solubility is introduced, self-assembled structures of the MJPs will be initiated.…”

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confidence: 99%

Manipulation of Self-Assembled Nanostructure Dimensions in Molecular Janus Particles

et al. 2016

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The ability to manipulate self-assembly of molecular building blocks is the key to achieving precise "bottom-up" fabrications of desired nanostructures. Herein, we report a rational design, facile synthesis, and self-assembly of a series of molecular Janus particles (MJPs) constructed by chemically linking α-Keggin-type polyoxometalate (POM) nanoclusters with functionalized polyhedral oligomeric silsesquioxane (POSS) cages. Diverse nanostructures were obtained by tuning secondary interactions among the building blocks and solvents via three factors: solvent polarity, surface functionality of POSS derivatives, and molecular topology. Self-assembled morphologies of KPOM-BPOSS (B denotes isobutyl groups) were found dependent on solvent polarity. In acetonitrile/water mixtures with a high dielectric constant, colloidal nanoparticles with nanophase-separated internal lamellar structures quickly formed, which gradually turned into one-dimensional nanobelt crystals upon aging, while stacked crystalline lamellae were dominantly observed in less polar methanol/chloroform solutions. When the crystallizable BPOSS was replaced with noncrystallizable cyclohexyl-functionalized CPOSS, the resulting KPOM-CPOSS also formed colloidal spheres; however, it failed to further evolve into crystalline nanobelt structures. In less polar solvents, KPOM-CPOSS crystallized into isolated two-dimensional nanosheets, which were composed of two inner crystalline layers of Keggin POM covered by two monolayers of amorphous CPOSS. In contrast, self-assembly of KPOM-2BPOSS was dominated by crystallization of the BPOSS cages, which was hardly sensitive to solvent polarity. The BPOSS cages formed the crystalline inner bilayer, sandwiched by two outer layers of Keggin POM clusters. These results illustrate a rational strategy to purposely fabricate self-assembled nanostructures with diverse dimensionality from MJPs with controlled molecular composition and topology.

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Preparation and Characterization of Polyhedral Oligosilsesquioxanes

Cited by 24 publications

References 441 publications

Synthesis of Tetrachloro, Tetraiodo, and Tetraazido Double-Decker Siloxanes

Synthesis of Tetrachloro, Tetraiodo, and Tetraazido Double-Decker Siloxanes

Synthesis and Characterization of Functionalizable Silsesquioxanes with Ladder-type Structures

Manipulation of Self-Assembled Nanostructure Dimensions in Molecular Janus Particles

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