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

摘要

A range of supramolecular complexes of O3S2-donor (L-1-L-3) and O2S3-donor (L-4) macrocycles with different ring sizes (L-1: 16-membered, L-2: 17-membered, L-3 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 L-1, L-3, and L-4 with the silver(I) salts (BF4- and CF3COO-) afforded four complexes 1-4 with different topologies: two endocyclic mononuclear complexes [Ag(L-1)NO3] (1) and [Ag(L-1)]BF4 (2), and two exocyclic complexes [Ag(L-3)(CF3COO)](n) (3) and [Ag-2(L-4)(2)(CF3COO)(2)] (4) with a two-dimensional (2D) coordination network and cyclic dimer structures, respectively. In the reactions with copper(I) iodide, L-1-L-4 afforded the Cu4I4-cubane linked 2D coordination polymer {[(Cu4I4)(L-1)(2)]center dot CH2Cl2}(n) (5), one-dimensional (1D) tubular coordination polymer {[(Cu4I4)(L-2)(2)]center dot 0.8CH(2)Cl(2)center dot 0.2CH(3)CN}(n) (6), Cu2I2-rhomboid linked 2D coordination polymer [(Cu2I2)(L-3)(2)](n) (7), and 2D coordination polymer [(Cu2I2)(L-4)(2)](n) (8), respectively. The reactions of the above ligands with mercury(II) salts (I- and SCN-) gave a cyclic dimer complex [Hg-2(L-3)(2)I-4] (9), mononuclear complex [Hg(L-4)I-2] (10), and 2D coordination polymer [Hg-2(L-3)(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.