Macrocyclic Inclusion Complexes. Synthesis, X-ray Structural Analysis, and Formation of Mono- and Dinuclear Transition-Metal Complexes of Dipyridino Crown Ethers

Article abstract of DOI:10.1021/jo00282a027

The synthesis of crown ether derivatives containing the dipyridino subunit is described.Direct nucleophilic displacement by the glycolates of di-, tri-, tetra-, penta-, and hexaethylene glycol on 6,6'-bis(chloromethyl)-2,2'-dipyridine resulted in an extensive series of macrocycles; the addition of Co(II), Cu(II), Zn(II), and Pd(II) salts to the 1:1- and 2:2-macrocycles generated the corresponding complexes.X-ray crystallography confirmed the structure of the 2:2-macrocycle derived from diethylene glycol as well as the related unsymmetrical derivative arising from glycol fragmentation.The ligands were fully characterized by 1H NMR spectroscopy, and a europium shift study was conducted on a representative 1:1-macrocycle in order to establish the preferred site of complexation.