title: Heterodinuclear metal arrangement in a flat macrocycle with two chemically-equivalent metal chelating sites.
abstract: A phenanthroline-based macrocycle 1 has been newly developed which has two chemically equivalent metal chelating sites within the spatially restricted cavity for dinuclear metal arrangement. The macrocycle 1 reacts with Zn(CF(3)CO(2))(2) or ZnCl(2) to form homodinuclear Zn(II)-complexes. A single-crystal X-ray structural analysis of the resulting Zn(2)1(CF(3)CO(2))(4) determined the complex structure in which two Zn(II) ions are bound by two phenanthroline sites and two CF(3)CO(2)(-) ions bind to each Zn(II) ion in a tetrahedral geometry. Similarly, a homodinuclear Cu(I)-macrocycle was formed from 1 and Cu(CH(3)CN)(4)BF(4). Notably, from 1 and an equimolar mixture of Cu(CH(3)CN)(4)BF(4) and Zn(CF(3)CO(2))(2), a heterodinuclear Cu(I)-Zn(II)-macrocycle was exclusively formed in high yield (>90%) because of the relatively low stability of the dinuclear Cu(I)-macrocycle. A heterodinuclear Ag(I)-Zn(II)-macrocycle was similarly formed with fairly high selectivity from a mixture of Ag(I) and Zn(II) ions. Such selective heterodinuclear metal arrangement was not observed with other combinations of M-Zn(II) (M = Li(I), Mg(II), Pd(II), Hg(II), La(III), and Tb(III)).
authors.affiliation: Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
authors.forename: Masumi
authors.initials: M
authors.lastname: Kuritani
authors.forename: Shohei
authors.initials: S
authors.lastname: Tashiro
authors.forename: Mitsuhiko
authors.initials: M
authors.lastname: Shionoya