A new potential model system for silicon monoxide (SiO) is synthesized by the interlinkage of an unsaturated silicon cluster (siliconoid) with a polyhedral silsequioxane cage. Two derivatives with variable linker size are obtained by the corner‐capping reaction of Ph7T7(ONa)3 with a trichlorosilane featuring a remote benzylic chloride functionality and the subsequent nucleophilic substitution of the latter by the anionic hexasilabenzpolarene‐type Si6 siliconoid. Based on the recently proposed heterogeneous cluster model for the SiO structure, the stoichiometry between silicon and oxygen reiterates the suboxidic interface of the nano‐composite in a Si : O ratio of 14 : 12.
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