Controllable Preparation and Optical Limiting Properties of POSS-Based Functional Hybrid Nanocomposites with Different Molecular Architectures

Abstract

A series of soluble polyhedral oligomeric silsesquioxane (POSS) based inorganic−organic hybrid nonlinear optical materials with different architectures, such as dumbbell-type, bead-type and network-type structure, were prepared based on the hydrosilylation addition reaction of multifunctional octahydridosilsesquioxane (T 8 H ) with different azobenzene chromophore monomers. These resultant hybrid composites are soluble in common organic solvents such as tetrahydrofuran, toluene, and chloroform, and exhibit good film-forming ability. Their structures and properties were characterized and evaluated with IR, 1H NMR, 29Si NMR, TGA, DSC, optical limiting measurement and Z-scan technique, respectively. The results show that the structure of these resultant hybrids can be effectively tuned by simply varying the feed ratio and molecular structure of organic chromophore monomers. The incorporation of inorganic POSS into organic azobenzene chromophore has endowed the hybrids with well optical limiting properties and high thermal stability. Simultaneously, the relationship between molecular structure and properties of these hybrids were investigated in detail.

Dumbbell-shaped polyhedral oligomeric silsesquioxanes/polystyrene nanocomposites: The influence of the bridge rigidity on the resistance to thermal degradation

“…The properties of obtained POSSs (geometry, length, rigidity and functionality) can be tuned by changing opportunely the organic bridge. 32,33 Even though only few papers have been published on bridged POSSs, [34][35][36] the results obtained until now seem to indicate that these compounds are thermally more stable than unbridged POSSs. 37 Recently, we synthesized two series of dumbbellshaped POSSs (the first one with aliphatic bridges and the second one with aromatic bridges) and assessed their resistance to thermal degradation.…”

Novel elastomer‐dumbbell functionalized POSS composites: Thermomechanical and Morphological Properties

“…Functionalized POSS was added to the solution and subjected to ultrasonic disruption (10 min, 25 C, 20 kHz) to ensure even distribution of the filler throughout the matrix. The solution was poured into an excess of cold methanol to precipitate the nanocomposite material and to restrict filler migration.…”

“…Another specific architectural structure is dumbbell-shaped (telechelic) POSS, consisting of two POSS ''weights'' connected chemically by an alkyl, polymer, or similar chain ''barbell.'' These structures have received relatively little attention, 24,25 despite exhibiting enhanced thermal stability, solubility, and film-forming properties. Mather and coworkers [26][27][28] have synthesized telechelic polymers consisting of a poly(ethylene glycol) bridges with POSS bonded to the chain end groups, observing changes in crystallization behavior, thermal degradation, and surface properties.…”

Highly efficient and stable solid-state luminescent nanohybrids: Precise architecture and enhancement mechanism

“…[18][19][20][21][22] In our recent work, some functional POSSbased hybrid materials with low dielectric constant or enhanced nonlinear optical properties were reported. [22][23][24][25][26] In this work, a well-defined 3D nanoscale dendritic hybrid, octakis(4-(9,9-dibutylfluorene)-1-methyl)-1,2, 3-triazole-(dimethylsiloxy)octa-silsequioxane (POSSAF) (Sch. 1) has been designed and precisely prepared via click chemistry.…”