Hard and Soft Metal Complexes of Calix[4]-bis-monothiacrown-5: X‑ray and NMR Studies of Discrete Homodinuclear Complexes and a Heteromultinuclear Network

Endocyclic homodinuclear complexation and endo/exocyclic heteronuclear networking of calix[4]-bis-monothiacrown-5 (L) are reported. First, dipotassium­(I) and disilver­(I) complexes of L were isolated and their solid state structures characterized. To probe the complexation behavior for these same systems in solution, the competition between potassium­(I) and silver­(I) for L was monitored by 1H NMR. Potassium­(I) showed a higher affinity to L than silver­(I) both in the solid and solution states. The reaction of L with KI in the presence of HgI2 afforded a two-dimensional coordination polymer with the endocyclic dipotassium­(I) complex linked by an exocyclic mercury­(II) iodide cluster backbone.本文报道了杯[4]-双-单硫杂冠醚-5（calix[4]-bis-monothiacrown-5，记为L）的环内同双核络合以及环内/环外异核网络化行为。首先，我们分离得到了配体L的二钾(I)配合物与二银(I)配合物，并对其固态结构进行了表征。为探究该类体系在溶液中的配位行为，我们通过1H核磁共振（1H NMR）监测了钾(I)与银(I)对配体L的竞争配位过程。实验结果表明，无论是在固态还是溶液状态下，钾(I)对配体L的结合亲和力均高于银(I)。将配体L与碘化钾在碘化汞(II)存在下反应，得到了一种二维配位聚合物，该聚合物以环内二钾(I)配合物为结构单元，通过环外碘化汞(II)簇作为骨架实现连接。