Supramolecular Silver(I), Copper(I), and Mercury(II) Complexes with Thiamacrocycles Exhibiting Different Types of Endo- or Exocoordination Modes: From Monomer and Dimer to One-Dimensional and Two-Dimensional Polymers

A range of supramolecular complexes of O3S2-donor (L1-L3) and O2S3-donor (L4) macrocycles with different ring sizes (L1: 16-membered, L2: 17-membered, L3 and L4: 18-membered) were synthesized and structurally characterized. For the 11 complexes (1–11), the structural topologies and the types of coordination modes including mono- to multinuclear and endo- to exocyclic ones via M–S bonds have been discussed in terms of the possible exocoordination modes proposed. The reactions of L1, L3, and L4 with the silver­(I) salts (BF4– and CF3COO–) afforded four complexes 1–4 with different topologies: two endocyclic mononuclear complexes [Ag­(L1)­NO3] (1) and [Ag­(L1)]­BF4 (2), and two exocyclic complexes [Ag­(L3)­(CF3COO)]n (3) and [Ag2(L4)2­(CF3COO)2] (4) with a two-dimensional (2D) coordination network and cyclic dimer structures, respectively. In the reactions with copper­(I) iodide, L1–L4 afforded the Cu4I4-cubane linked 2D coordination polymer {[(Cu4I4)­(L1)2]­·CH2Cl2}n (5), one-dimensional (1D) tubular coordination polymer {[(Cu4I4)­(L2)2]­·0.8CH2Cl2­·0.2CH3CN}n (6), Cu2I2-rhomboid linked 2D coordination polymer [(Cu2I2)­(L3)2]n (7), and 2D coordination polymer [(Cu2I2)­(L4)2]n (8), respectively. The reactions of the above ligands with mercury­(II) salts (I– and SCN–) gave a cyclic dimer complex [Hg2(L3)2I4] (9), mononuclear complex [Hg­(L4)­I2] (10), and 2D coordination polymer [Hg2(L3)­(SCN)4]n (11). The structural comparison of the complexes reveals that even small structural variations in the macrocycles result in a dramatic impact on the topology of the supramolecular products mainly due to the different coordination modes.