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The dynamic covalent self-assembly of 14 units of bis(perfluorocatecholato)silane leads to [Si(O2 C6 F4 )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. F