The figure-of-eight twist to macrocycles: preorganization, self-organization and dynamics

Large macrocyclic rings (30- to 36-membered) with two dithiadiimine donor s ets and two para- or meta-phenylene spacer groups undergo copper(I) induced folding with pi stacking of the two benzene spacer groups, The type of fol ding (twisted to a helical or squeezed to an achiral macrocyclic shape) and the stability of the dicopper(I) compounds are analysed as a function of t he ligand structure, the solid state structures, solution equilibria and dy namics and the comparison of the observed data with computed structures and conformational equilibria, Preliminary preparative studies suggest that de rivatives with the observed structural motifs may be used to build heterome tallic oligonuclear arrays.