Self-assembly of triangular and hexagonal molecular necklaces

The formation of catenated systems can be simplified greatly if one or more rings are generated via self-assembly. Herein we exploit the orthogonality of coordination-driven self-assembly and crown-ether host-guest complexation to obtain a [4]molecular necklace and a [7]molecular necklace based on a well-developed recognition motif of 1,2-bis(pyridinium)ethane/dibenzo[24]crown- 8. By adapting the bis(pyridinium) motif into the backbone of a donor building block, the resulting semirigid dipyridyl species can serve both as a structural element in the formation of metallacycles and as a site for subsequent host-guest chemistry. The pseudolinear nature of the donor precursor lends itself to the formation of triangular and hexagonal central metallacycles based on the complementary acceptor unit used. This exemplary system organizes up to 18 molecules from three unique species in solution to afford a single supramolecular ensemble.