Networking of macrocycles: 1D and 2D coordination polymers of dithia-18-crown-6 with copper(ii) and copper(i)

Abstract

Cu^I and Cu^II coordination polymers of 1,10-dithia-18-crown-6 (L) with unusual networking modes involving an exocyclic coordination are presented. The reaction of L with copper(II) nitrate gave a unprecedented ladder-type 1D coordination polymer {[(L_OXOX)Cu₂(NO₃)₂(H₂O)₄](L_OXOX)(NO₃)₂·2H₂O}_n (1) via strong Cu^II–O_sulfoxide bonds because L was oxidized to the disulfoxide macrocycle (L_OXOX) under the present conditions. Meanwhile the parallel reaction of copper(I) iodide with L in the presence of cobalt(II) perchlorate yielded a mixture of an emissive 2D network product [(Cu₄I₄)(L)₂]_n (2) linked with cubane-type Cu₄I₄ clusters and a non-emissive 1D coordination polymer {[(Cu₂I₂)(L)₂][Co(H₂O)₆](ClO₄)₂·0.5H₂O}_n (3) linked with rhomboidal Cu₂I₂ cores. In 3, hexaaquacobalt(II) complexes, anions and water molecules also exist and stabilize the 1D macrocyclic network through H-bonds.