Dynamic [2]catenanes based on a hydrogen bonding-mediated bis-zinc porphyrin foldamer tweezer: A case study

Article abstract of DOI:10.1021/jo062523g

(Chemical Equation Presented) This paper describes the self-assembly of a new class of three-component dynamic [2]catenanes, which are driven or stabilized by intramolecular hydrogen bonding, coordination, and electrostatic interaction. One of the component molecules 2, consisting of an aromatic oligoamide spacer and two peripheral zinc porphyrin units, was designed to adopt a folded preorganized conformation, which is stabilized by consecutive intramolecular three-centered hydrogen bonds. Component molecule 3 is a linear secondary ammonium bearing two peripheral pyridine units, which was designed to form a 1:1 complex with 24-crown-8 (5). The ¹H NMR and UV-vis experiments in CDCl₃-CD₃CN (4:1 v/v) revealed that, due to the preorganized U-shaped feature, 2 could efficiently bind 3 through the cooperative zinc-pyridine coordination to generate highly stable 1:1 complex 2·3. Adding 5 to the 1:1 solution of 2 and 3 led to the formation of dynamic three-component [2]catenane 2·3·5 as a result of the threading of 3 through 5. ¹H NMR studies indicated that in the 1:1:1 solution (3 mM) [2]catenane 2·3·5 was generated in 55% yield at 25°C. The yield was increased with the reduction of the temperature and [2]catenane could be produced quantitatively in a 1:1:2 solution ([2] = 3 mM) at -13°C. Replacing 3 with 1,2-bis(4,4′-bipyridinium)ethane (4) in the three-component solution could also give rise to similar dynamic [2]-catenane 2·4·5 albeit in slightly lower yield.