Allosteric deprogramming of a trinuclear heterometallic helicate

Two multidentate ditopic ligands L1 and L2 which contain both N-donor and crown ether units have been synthesised. The potentially octadentate ligand L1 forms a trinuclear heterometallic double helicate with Cu(I) and Zn(II) (Zn2Cu(L1)2](5+)), whereas L2 forms a tetranuclear heterometallic double helicate with the same metal ions (Zn2Cu2(L2)2](6+)). Both species have been characterised by (1)H NMR, ESI-MS and single crystal X-ray crystallography. Reaction of Zn2Cu2(L2)2](6+) with Ba(2+) results in the coordination of the crown ether units giving the simple barium coordinated species Zn2Cu2(L2)2Ba2](10+). However, reaction of Zn2Cu(L1)2](5+) with Ba(2+) deprograms the ligand and results in the formation of a mixture of species.