Hexanuclear and Trinuclear Metal Complexes of a Giant Octadecaaza Macrocycle.

A large macrocyclic ligand containing six pyridine fragments and six diaminocyclopentane fragments is able to form hexanuclear Zn(II) and Ni(II) complexes as well as a trinuclear Zn(II) complex. X-ray crystal structures of these complexes indicate quite different ligand conformations. In the hexanuclear Zn(II) derivative with chloride counteranions metal ions have a distorted-trigonal-bipyramidal geometry and occupy loop sections formed by the highly folded macrocycle, which adopts a globular shape. In the hexanuclear Ni(II) derivative with nitrate counteranions metal ions exhibit a distorted-octahedral geometry and the ligand conformation is much more open, while in the trinuclear Zn(II) complex the macrocycle wraps around the octahedral metal ions. The last highly entangled conformation of the trinuclear complex is also present in solution, as confirmed by the NOESY spectra. The NMR data indicate that the hexanuclear Zn(II) complex partially dissociates in water solutions to form the trinuclear complex, while the 1H NMR titration of the free macrocycle with zinc(II) chloride indicates that the formation of a trinuclear complex corresponds to cooperative binding of metal ions.