Silver(I) and Copper(I) Coordination Polymers Based on Thiaoxa‐Macrocycles

Two S 2 O 2 ‐macrocycles with different ring size ( L 1 : 17‐ and L 2 : 18‐membered) were synthesised and structurally characterised by X‐ray analysis. Reactions of L 1 and L 2 with silver(I) salts (ClO 4 – and NO 3 – ) afforded respective ligand‐ and/or anion‐directed complexes 1 – 4 with different topologies; single‐stranded 1D coordination polymer [Ag L 1 (ClO 4 )(DMSO)] n ( 1 ), double‐stranded 1D coordination polymer {[Ag 2 ( L 1 ) 2 (NO 3 ) 2 ] · DMSO} n ( 2 ), cyclic dimer [Ag 2 ( L 2 ) 2 (ClO 4 ) 2 ] · CH 2 Cl 2 · CH 3 OH ( 3 ) and 2D polymeric sheet [Ag( L 2 )NO 3 ] n ( 4 ). Meanwhile, reactions of these two ligands with copper(I) iodide afforded 1D ( 5 ) and 2D ( 6a ) coordination polymers linked with a rhomboid‐type Cu–I 2 –Cu unit, respectively. The formation of such discrete and continuous supramolecular complexes is discussed in terms of discrimination of the anion effect, ligand flexibility as well as interligand π‐π stacking interaction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)