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
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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.
一系列由O3S2给体大环（L1~L3）与O2S3给体大环（L4）构成的超分子配合物被成功合成并完成结构表征，上述大环具有不同的环尺寸：L1为16元环、L2为17元环、L3与L4为18元环。针对11个目标配合物（1~11），本文基于所提出的潜在外配位模式，讨论了其结构拓扑类型，以及涵盖单核至多核、环内至环外配位（通过金属-硫（M–S）键形成）在内的各类配位模式。配体L1、L3与L4分别与银(I)盐（四氟硼酸根BF4–与三氟乙酸根CF3COO–）反应，得到4个具有不同拓扑结构的配合物1~4：分别为两个环内单核配合物[Ag(L1)NO3]（1）与[Ag(L1)]BF4（2），以及两个分别具有二维（2D）配位网络与环状二聚体结构的环外配合物[Ag(L3)(CF3COO)]n（3）与[Ag2(L4)2(CF3COO)2]（4）。当与碘化亚铜反应时，配体L1~L4分别得到如下产物：由Cu4I4立方烷连接的二维配位聚合物{[(Cu4I4)(L1)2]·CH2Cl2}n（5）、一维（1D）管状配位聚合物{[(Cu4I4)(L2)2]·0.8CH2Cl2·0.2CH3CN}n（6）、由Cu2I2菱形单元连接的二维配位聚合物[(Cu2I2)(L3)2]n（7），以及二维配位聚合物[(Cu2I2)(L4)2]n（8）。上述配体与汞(II)盐（碘离子I–与硫氰酸根SCN–）反应时，分别得到环状二聚体配合物[Hg2(L3)2I4]（9）、单核配合物[Hg(L4)I2]（10），以及二维配位聚合物[Hg2(L3)(SCN)4]n（11）。对上述配合物的结构对比研究表明，即使大环仅存在微小的结构差异，也会对超分子产物的拓扑结构产生显著影响，这一现象主要源于不同配位模式的差异。
