[Si(O<sub>2</sub>C<sub>6</sub>F<sub>4</sub>)<sub>2</sub>]<sub>14</sub>: Self‐Assembly of a Giant Perfluorinated Macrocyclic Host by Low‐Barrier Si−O Bond Metathesis
Deborah Hartmann, Lutz Greb
Abstract
Abstract The dynamic covalent self‐assembly of 14 units of bis(perfluorocatecholato)silane leads to [Si(O 2 C 6 F 4 ) 2 ] 14 —the first giant perfluorinated macrocycle. The oligomerization process is monitored spectroscopically, and the macrocycle analyzed by single‐crystal X‐ray diffraction. The molecule forms a rigid cavity that can host two o ‐closo‐dodecacarboranes. Computations rationalize the consistent and reproducible formation of the 14mer and disclose a non‐catalyzed Si−O/ Si−O σ‐bond metathesis with an exceptionally low energetic barrier. For the first time, the most prevalent linker in our geosphere‐SiO 4 ‐is disposed to construct a shape‐defined crystalline macromolecule.
Topics & Concepts
CrystallographySilaneMoleculeMacromoleculeCovalent bondSelf-assemblyMetathesisMaterials scienceChemistryCrystal (programming language)NanotechnologyOrganic chemistryPolymerPolymerizationBiochemistryProgramming languageComputer scienceSupramolecular Chemistry and ComplexesSupramolecular Self-Assembly in MaterialsLuminescence and Fluorescent Materials