Stability constants have been measured for a series of ligands based o
n a 2,2'-(pyridine-2,6-diyl)bis[1H-benzimidazole] unit which forms din
uclear double-stranded helical complexes with copper(I). Variation of
different structural parameters confirms the importance of the coordin
ate bond, the stacking interactions, and the weakly bridging pyridine
units observed by X-ray crystallography. The stabilities of the comple
xes depend strongly on the solvent, and in MeCN, which is a good solve
nt for copper(I), the complexes are less stable and assemble in a step
wise manner. The interconversion of the enantiomers may be followed by
H-1-NMR and takes place on a millisecond time scale around room tempe
rature. The trends in lability are similar to those found for the stab
ility of the complexes.