THE FIGURE-OF-EIGHT TWIST TO MACROCYCLES : PREORGANIZATION, SELF-ORGANIZATION AND DYNAMICS

Large macrocyclic rings (30- to 36-membered) with two dithiadiimine donor sets and two para- or meta-phenylene spacer groups undergo copper(I) induced folding with π stacking of the two benzene spacer groups. The type of folding (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 the ligand structure, the solid state structures, solution equilibria and dynamics and the comparison of the observed data with computed structures and conformational equilibria. Preliminary preparative studies suggest that derivatives with the observed structural motifs may be used to build heterometallic oligonuclear arrays.