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

Abstract

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 poly...