This article describes hybrid materials and systems in which the core integrity of inorganic nanobuilding blocks (NBBs) is preserved and reviews the main synthetic procedures presented in the literature. The relation between the NBB and the resulting hybrid networks is discussed for several striking examples:  silicon and tin oxo clusters, polyoxometalates, and transition metal−oxo-based clusters. This approach is extended to nanoparticule-based hybrids. The chemical strategies offered by the coupling of soft chemistry processes and this approach based on functional NBBs allows, through an intelligent and tuned coding, to develop a new vectorial chemistry that is able to direct the assembly of a large variety of structurally well-defined clusters or nanoparticles into complex architectures.

Designed Hybrid Organic−Inorganic Nanocomposites from Functional Nanobuilding Blocks

This review describes the synthesis and properties of homopolymers and copolymers of monomers containing inorganic–organic hybrid polyhedral oligomeric silsesquioxane (POSS) structures. Monomers, such as styryl-POSS, methacrylate-POSS, norbornyl-POSS, vinyl-POSS, epoxy-POSS, and siloxane-POSS, are included. Both monofunctional and multifunctional monomers are included. Thermoplastic and thermoset systems are considered. Thermal, rheological, and dynamic mechanical properties are described. The synthesis of POSS macromers (monomers) is briefly described. POSS chemicals have been used to prepare nanosized designed novel composites with a variety of potential applications. This review, covering 111 references, is descriptive and not designed to be totally comprehensive. However, the major existing reviews of certain subtopics are noted, allowing the reader to gain a general introduction while providing the information to permit more comprehensive coverage.

Polyhedral Oligomeric Silsesquioxane (POSS) Polymers and Copolymers: A Review

Tailoring of porous materials involves not only chemical synthetic techniques for tailoring microscopic properties such as pore size, pore shape, pore connectivity, and pore surface reactivity, but also materials processing techniques for tailoring the meso- and the macroscopic properties of bulk materials in the form of fibers, thin films, and monoliths. These issues are addressed in the context of five specific classes of porous materials:  oxide molecular sieves, porous coordination solids, porous carbons, sol−gel-derived oxides, and porous heteropolyanion salts. Reviews of these specific areas are preceded by a presentation of background material and review of current theoretical approaches to adsorption phenomena. A concluding section outlines current research needs and opportunities.

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Tailored Porous Materials

Hetero- and Metallasiloxanes Derived from Silanediols, Disilanols, Silanetriols, and Trisilanols

A critical analysis of the present state of synthetic methods and mechanisms of the formation of polyhedral oligosilsesquioxanes and their homo derivatives is given. The data available on the structure, physico-chemical properties, reactivity, and application of the above compounds are summarized and systematized.

Paul I. Prescott

Papers

Preparation and Characterization of the Lower Equilibrated Phenylsilsesquioxanes

Intramolecular Interactions between Nonbonded Chromophores. The Spectra of Some Phenylsilanes and Siloxanes