Mesoporous organic-inorganic hybrid materials, a new class of materials characterized by large specific surface areas and pore sizes between 2 and 15 nm, have been obtained through the coupling of inorganic and organic components by template synthesis. The incorporation of functionalities can be achieved in three ways: by subsequent attachment of organic components onto a pure silica matrix (grafting), by simultaneous reaction of condensable inorganic silica species and silylated organic compounds (co-condensation, one-pot synthesis), and by the use of bissilylated organic precursors that lead to periodic mesoporous organosilicas (PMOs). This Review gives an overview of the preparation, properties, and potential applications of these materials in the areas of catalysis, sorption, chromatography, and the construction of systems for controlled release of active compounds, as well as molecular switches, with the main focus being on PMOs.

Mesoporous organic–inorganic hybrid materials, a new class of materials characterized by large specific surface areas and pore sizes between 2 and 15 nm, have been obtained through the coupling of inorganic and organic components by template synthesis. The incorporation of functionalities can be achieved in three ways: by subsequent attachment of organic components onto a pure silica matrix (grafting), by simultaneous reaction of condensable inorganic silica species and silylated organic compounds (co‐condensation, one‐pot synthesis), and by the use of bissilylated organic precursors that lead to periodic mesoporous organosilicas (PMOs). This Review gives an overview of the preparation, properties, and potential applications of these materials in the areas of catalysis, sorption, chromatography, and the construction of systems for controlled release of active compounds, as well as molecular switches, with the main focus being on PMOs.

Durch die Verknüpfung anorganischer und organischer Bausteine mithilfe der templatgesteuerten Synthese gelangt man zu einer neuen Materialklasse, den mesoporösen organisch‐anorganischen Hybridmaterialien, die sich durch große spezifische Oberflächen sowie Porengrößen zwischen 2 und 15 nm auszeichnet. Das Einbringen der organischen Reste lässt sich auf drei Wegen erreichen: Durch die nachträgliche Anbindung organischer Komponenten an eine reine Silicamatrix (Pfropfung), durch die gleichzeitige Umsetzung kondensationsfähiger anorganischer Silicaspezies und silylierter organischer Verbindungen (Cokondensation, Eintopfsynthese) und durch die Verwendung bissilylierter organischer Vorstufen, die zu periodisch mesoporösen Organosilicas (PMOs) führt. Dieser Aufsatz gibt einen Überblick über die Herstellung, die Eigenschaften sowie die Anwendungsmöglichkeiten im Bereich der Katalyse, Sorption, Chromatographie, des Aufbaus von Systemen zur kontrollierten Wirkstoffabgabe sowie molekularer Schalter, wobei das Hauptaugenmerk auf PMOs liegt.

Periodic mesoporous organosilicas (PMOs) represent a new class of organic-inorganic hybrid materials suitable for a broad range of applications such as chromatography, catalysis, sensing and microelectronics. Unlike in organic functionalized mesoporous silica phases obtained via grafting or co-condensation procedures the organic groups in PMOs are direct parts of the 3D framework structure, thus giving raise to enormous possibilities to tune their chemical and physical properties in designated ways by varying the structure of the precursors. In this review the distinctive features of PMOs are discussed, the latest developments concerning compositions, structures, morphologies and potential applications are figured out and finally a brief outlook of future aspects is given.

The synthesis of a 2D hexagonal highly ordered periodic mesoporous 1,4-divinylbenzene-bridged organosilica (PMO) with crystal-like pore walls is reported. Both functionalities are realized by utilization of one single precursor (1,4-bis-((E)-2-(triethoxysilyl)vinyl)benzene (BTEVB) which was synthesized via Pd-catalyzed double Heck coupling of 1,4-dibromobenzene with vinyltriethoxysilane. Solid state 29Si MAS NMR and FT-IR spectroscopy confirms that during the hydrothermal PMO synthesis and subsequent extraction procedure (i) no Si−C bond cleavage occurred and (ii) the organic bridge is preserved. The novel PMO material with a pore diameter of 2.6 nm, a molecular scale periodicity of 1.19 nm within the pore walls, and a specific surface area of S BET = 730 m2/g offer various opportunities for further chemical modification within the mesopores as shown by bromination reactions.

Like Honeycomb is how the pore structures of silica‐based mesoporous organic–inorganic hybrid materials often appear. In the Review on page 3216 ff., M. Fröba and co‐workers give an overview of their preparation. The cover picture shows hybrids whose pores are functionalized with cyclam (ligand), sulforhodamine B (laser die), and a cinchona derivative (for heterogeneous asymmetric catalysis). Particular attention is given to the class of periodic mesoporous organosilicas (PMOs).

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