Pd(II) Coordination Sphere Engineering: Pyridine Cages, Quinoline Bowls, and Heteroleptic Pills Binding One or Two...

Fullerenes 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.