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 (1)H 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.

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