The dynamic covalent chemistry (DCvC) of the Si−O bond holds unique opportunities, but has rarely been employed to assemble discrete molecular architectures. This may be due to the harsh conditions required to initiate exchange reactions at silicon in aprotic solvents. Herein, we provide a comprehensive experimental and computational account on the reaction of trialkoxysilanes with alcohols and identify mild conditions for rapid exchange in aprotic solvents. Substituent, solvent and salt effects are uncovered, understood and exploited for the construction of sila‐orthoester cryptates. A sharp, divergent pH‐response of the obtained cages renders this substance class attractive for future applications well beyond host‐guest chemistry, for instance, in drug delivery.

The dynamic covalent chemistry (DCvC) of the SiÀ O bond holds unique opportunities, but has rarely been employed to assemble discrete molecular architectures. This may be due to the harsh conditions required to initiate exchange reactions at silicon in aprotic solvents. Herein, we provide a comprehensive experimental and computational account on the reaction of trialkoxysilanes with alcohols and identify mild conditions for rapid exchange in aprotic solvents. Substituent, solvent and salt effects are uncovered, understood and exploited for the construction of silaorthoester cryptates. A sharp, divergent pH-response of the obtained cages renders this substance class attractive for future applications well beyond host-guest chemistry, for instance, in drug delivery.

The crystal structure of the title compound was determined using electron diffraction data collected in continuous rotation mode. The structure was successfully solved and refined kinematically in the monoclinic space group P21/c, with a Z value of 2 and Z′ value of 0.5. Within the crystal structure, the entire molecule is predominantly flat. The molecular packing exhibits a herringbone pattern, distinct from that of the unchlorinated analogue molecule. The largest facet of the crystals, which faces the supporting carbon film, is designated as (0 1 ‾ 1 ‾ $\bar{1}\bar{1}$ ).