A Covalent Organic Cage Compound Acting As A Supramolecular Shadow Mask For The Regioselective Functionalization Of C-60

A trigonal-bipyramidal covalent organic cage compound serves as an efficient host to form stable 1 : 1-complexes with C-60 and C-70. Fullerene encapsulation has been comprehensively studied by NMR and UV/Vis spectroscopy, mass spectrometry as well as single-crystal X-ray diffraction. Exohedral functionalization of encapsulated C-60 via threefold Prato reaction revealed high selectivity for the symmetry-matched all-trans-3 addition pattern.