The new acyclic tetraoxime ligand H4L1, having two allyl groups at the terminal benzene rings, was designed and synthesized. The ligand H4L1 was converted to five kinds of the trinuclear complexes, [(LZn3)-Zn-1(OAc)(2)], [(LZn2La)-Zn-1(OAc)(3)], [(LZn2Ca)-Zn-1(OAc)(2)], [(LZn2Sr)-Zn-1(OAc)(2)], and [(LZn2Ba)-Zn-1(OAc)(2)]. The terminal allyl groups were introduced so that the olefin metathesis could convert the metal complexes into the dimeric macrocyclic ligand H8L3. The X-ray crystallographic analysis of the trinuclear complexes [(LZn3)-Zn-1(OAc)(2)(H2O)], [(LZn2La)-Zn-1(OAc)(3)(MeOH)], [(LZn2Ca)-Zn-1(OAc)(2)], and [(LZn2Sr)-Zn-1(OAc)(2)] revealed that the distances between the two allyl groups are 11-12 angstrom, which should be sufficient to suppress the intramolecular reaction leading to the monomeric macrocycle H4L2. Indeed, the olefin metathesis of the [(LZn2Ca)-Zn-1(OAc)(2)] and [(LZn2Sr)-Zn-1(OAc)(2)] followed by demetalation with dilute hydrochloric acid afforded the dimeric macrocycle H8L3 as the major product, while the reaction of the uncomplexed ligand H4L1 gave the monomeric macrocycle H4L2 as the major product. The complexation behavior of H8L3 at the two tetraoxime sites was investigated. Although the formation process of the hexanuclear zinc(II) complex [(LZn6)-Zn-3](4+) was complicated, the metal exchange of the two trinuclear zinc(II) units proceeded in a two-step fashion. The analysis of the spectral changes indicated the positive and negative cooperative effects on the double metal exchange with Ca2+ and Ba2+, respectively. The first metal exchange reactions with Ca2+ made the second metal exchange more favorable. Thus, the obtained dimeric macrocycle H8L3 has two tetraoxime coordination sites, whose complexation behavior is remotely affected by each other.