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.