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The chiral macrocyclic amines R-L and S-L derived from the 3 + 3 condensation of 2,6-diformylpyridine and (1R,2R)-1,2-diaminocyclohexane or (1S,2S)-1,2-diaminocyclohexane form enantiopure trinuclear Ni(ii) and Cu(ii) complexes [Ni 3 (L)(H 2 O) 2 Cl 5 ]Cl and [Cu 3 (L)Cl 4 ]Cl 2 and form the dinuclear complex [Zn 2 (L)Cl 2 ](ZnCl 4 ) with Zn(ii). The X-ray crystal structures of these complexes indicate remarkably different conformations of the ligand and different binding modes of the chloride anions. The structure of the copper(ii) derivative [Cu 3 (R-L)Cl 4 ]Cl 2 ·CH 3 CN·7.5(H 2 O) indicates unsymmetrical conformation of the macrocycle with three dissimilar pentacoordinate copper(ii) ions bridged by chloride; the structure of [Ni 3 (R-L)(H 2 O) 2 Cl 5 ]Cl·0.4CH 3 CN·4.2H 2 O is somewhat more symmetrical, with three Ni(ii) ions of distorted octahedral geometry, also bridged by a common chloride anion. On the other hand, the macrocycle is highly folded in [Zn 2 (R-L)Cl 2 ](ZnCl 4 )·CHCl 3 ·0.8CH 3 OH·3.7H 2 O, forming a cleft where the third Zn(ii) ion is held via electrostatic interactions as the ZnCl 4  2- anion. The magnetic data for [Cu 3 (R-L)Cl 4 ]Cl 2 indicate the coexistence of antiferromagnetic and ferromagnetic interactions within the quasi isosceles tricopper(ii) core (J = -85.6 cm -1 , j = 77.1 cm -1 ). Compound [Ni 3 (R-L)(H 2 O) 2 Cl 5 ]Cl shows the presence of weak antiferromagnetic coupling (J = -2.56 cm -1 , j = -1.54 cm -1 ) between the three Ni(ii) ions.

Multinuclear Ni(ii), Cu(ii) and Zn(ii) complexes of chiral macrocyclic nonaazamine