Solid‐State Self‐Assembly of Polymeric Double Helicates Leading to Linear Arrays of Silver(I) Ions and Reversible Strand/Double Helix Interconversion in Solution

Abstract

Reaction of a bent py-hyz-pym-hyz-pym 1 and of a linear py-hyz-py-hyz-pym 3 (py=pyridine; pym=pyrimidine; hyz=hydrazone) ligand strands with silver(I) tetrafluoroborate in CH(3)NO(2) generates double-helical dinuclear 2 and trinuclear 4 complexes. These complexes form polymeric, highly ordered solid-state structures, with wirelike, linear continuous or discontinuous polycationic Ag(n) (+) arrays with Ag--Ag distances of 2.78 to 4.42 A. Ligand 5, an isomer of 1, is found to yield a [2x2] grid-type complex 6. Titration experiments reveal the formation of linear rack-type dinuclear species from 1 and 5. Acid-base modulated, reversible interconversion between strand 1 and double helicate 2 may be achieved by using tren as a competing complexing agent (tren=N(CH(2)CH(2)NH(2))(3)). Progressive addition of silver(I) ions to a 1:1 mixture of 1 and 5 leads to the preferential formation of the double helicate 2 over the grid complex 6, illustrating a process of self-organisation with selection of the correct ligand.