Organic-inorganic hybrid nano-building blocks of aromatic nitro-, aldehyde-, and bromo-functionalized polyhedral oligomeric silsesquioxanes were easily prepared through nucleophilic substitutions, starting from the reactions between octakis(3-chloropropyl)octasilsesquioxane and phenoxide derivatives. These phenoxide anions not only supply the substitution functions to a silsesquioxane cage, but can also induce a cage-rearrangement leading to the formation of octa-, deca-, and dodecahedral silsesquioxane cages.

A novel synthetic method for the construction of a double-decker silsesquioxane from fluorosilanes was developed. Phenyl-substituted double-decker silsesquioxane was prepared under mild conditions by coupling difluorodiphenylsilane and a tetrasiloxanolate precursor. A similar reaction was performed using difluorovinylsilane, and a divinyl double-decker silsesquioxane was obtained. The one-step reaction of a functional difluorosilane containing an aminopropyl group afforded a novel double-decker silsesquioxane with two amino groups complexed with BF3, which can react with carboxylic acid anhydrides to afford an amide product. This synthetic method using difluorosilane is tolerant of a wide range of functional groups and is applicable to the synthesis of polycyclic silsesquioxanes bearing amino groups, which are difficult to directly obtain from dichlorosilane.

A new synthetic method for tricyclic laddersiloxanes, ladder‐type silsesquioxanes with defined structures, is developed based on intramolecular cyclization of hydrosilyl‐functionalized cyclic siloxanes. This method enables the construction of unprecedented laddersiloxanes with various ring sizes. Herein, the preparation of tricyclic laddersiloxanes containing 6‐8‐6‐, 8‐8‐8‐, or 12‐8‐12‐membered‐ring systems is reported. These products can be considered as bat‐shape siloxanes, owing to their rigid inorganic siloxane body with flexible oligosiloxane “wings” as side rings. The synthesized compounds are potential building blocks for well‐defined nanomaterials, porous materials, and host molecules.