Abstract
A ditopic 23-membered NO4S2-macrocycle (L) incorporating both semi-rigid and flexible binding sites was synthesized and its silver(I) and mercury(II) complexes exhibiting different stoichiometries and coordination modes were prepared. First, silver(I) perchlorate reacts with L to afford an endocyclic mononuclear complex [Ag(L)]ClO4 (1) in which the silver(I) ion locates at the semi-rigid binding site in the cavity. The solution study for the silver(I) complexation via the 1H NMR titration agrees with the corresponding solid state data that show the endo-mode. Interestingly, the reaction of L with HgI2 led to the isolation of two conformational isomers with a tetranuclear bis(macrocycle) composition, [(exoHgLI2)2(μ-Hg2I4)] (2a) and [(endoHgLI2)2(μ-Hg2I4)] (2b), which are dominated by the coordination modes of L toward the mercury(II) center. In both conformers, two exocyclic mercury(II) complex units (exoHgLI2)2 in 2a or two endocyclic complex units [(endoHgLI2)2 in 2b are linked by tetraiododimercury(II) core (μ-Hg2I4) to give a 4:2 (metal-to-ligand) stoichiometry. Based on the packing structures and high temperature experiment, the intermolecular interactions might be responsible for the formation of 2a and 2b which are kinetically and thermodynamic controlled, respectively.
Published Version
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