Chen, BinHolstein, Julian J.Horiuchi, ShinnosukeHiller, Wolf G.Clever, Guido H.2019-07-112019-07-112019-05-08http://hdl.handle.net/2003/3813310.17877/DE290R-20114Fullerenes and their derivatives are of tremendous technological relevance. Synthetic access and application are still hampered by tedious purification protocols, peculiar solubility, and limited control over regioselective derivatization. We present a modular self-assembly system based on a new low-molecular-weight binding motif, appended by two palladium(II)-coordinating units of different steric demands, to either form a [Pd2L14]4+ cage or an unprecedented [Pd2L23(MeCN)2]4+ bowl (with L1 = pyridyl, L2 = quinolinyl donors). The former was used as a selective induced-fit receptor for C60. The latter, owing to its more open structure, also allows binding of C70 and fullerene derivatives. By exposing only a fraction of the bound guests’ surface, the bowl acts as fullerene protecting group to control functionalization, as demonstrated by exclusive monoaddition of anthracene. In a hierarchical manner, sterically low-demanding dicarboxylates were found to bridge pairs of bowls into pill-shaped dimers, able to host two fullerenes. The hosts allow transferring bound fullerenes into a variety of organic solvents, extending the scope of possible derivatization and processing methodologies.enhttps://creativecommons.org/licenses/by/4.0/Supramolecular chemistrySelf assemblyCoordination cageCoordination bowlFullereneFunctionalizationFullerene separation540article (journal)