Characteristic features of formation, synthesis, and properties of binuclear zinc(II) helicates with alkyl-substituted 3,3′-bis(dipyrrolylmethenes)

Abstract

On the basis of spectrophotometric studies, it was demonstrated that complexation of hydrobromides of seven alkylated 3,3′-bis(dipyrrolylmethenes) (H 2 L · 2HBr) with zinc(II) acetate dihydrate in DMF (298.15 K) includes successive steps of formation of binuclear helicates of two types: [Zn 2 (AcO) 2 L] (heteroleptic single-helix complex) and [Zn 2 L 2 ] (homoleptic double-helix complex). An increase in the degree of alkylation of the pyrrole rings of the ligands from 4 to 10 methyl groups induces an increase of overall complexation constants from 7.60 to 13.73. The synthesis of helicates [Zn 2 L 2 ] was described. The products were studied by elemental analysis and IR, 1 H NMR, U/Vis, and fluorescence spectroscopy. The effect of the helicand structure and the solvent nature on the chromophore and fluorescence properties of [Zn 2 L 2 ] was discussed. The kinetic stability of zinc(II) with decamethyl-substituted 3,3′-bis(dipyrrolylmethene) in HCl-DMF medium was estimated.