Chirality transfer between hexaazamacrocycles in heterodinuclear rare earth complexes

Abstract

Both the chiral hexaazamacrocyle L1 based on trans-1,2-diaminocyclohexane and the achiral hexaazamacrocyle L2 based on ethylenediamine form lanthanide(III) dinuclear μ-hydroxo bridged complexes which have been characterized by NMR and CD spectroscopy. The homodinuclear complexes of the type [Ln₂(L1)₂(μ-OH)₂](NO₃)₄ (Ln = Nd^III, Eu^III, Tb^III and Yb^III) have been synthesized in the enantiopure form and the X-ray crystal structures of Nd^III, Eu^III and Yb^III derivatives have been determined. The heterodinuclear cationic complexes [Ln(L1)Ln′(L2)(μ-OH)₂X₂]ⁿ⁺ have been generated and characterized in solution by using the mononuclear complexes of L1 and L2 as substrates. While the formation of [LnLn′(L1)₂(μ-OH)₂X₂]ⁿ⁺ dinuclear complexes is accompanied by chiral narcissistic self-sorting, the formation of [Ln(L1)Ln′(L2)(μ-OH)₂X₂]ⁿ⁺ dinuclear complexes is accompanied by the sizable sociable self-sorting of macrocyclic units. The homodinuclear complexes [Y₂(L1)₂(μ-OH)₂X₂]ⁿ⁺ and [Ln₂(L2)₂(μ-OH)₂X₂]ⁿ⁺ (Ln = Dy^III, Pr^III and Nd^III) are CD silent in the visible region due to the lack of f–f transitions and the presence of an achiral ligand, respectively. In contrast, the heterodinuclear [Y(L1^S)Ln(L2)(μ-OH)₂X₂]ⁿ⁺ complexes give rise to CD signals arising from the f–f transitions because of the chirality transfer from the L1 macrocyclic unit to the L2 macrocyclic unit.