Calix[4]bis(thiacrown): assembly of an endocyclic disilver(I) complex and exocyclic 3D copper(I) coordination polymers.

Calix[4]bis(thiacrown-5) (L) with 1,3-alternating conformation was employed as a strong dinucleating ligand for the soft metal ions AgI and CuI. The reaction of L with AgPF6 afforded a discrete endo-coordinated disilver(I) complex 1, [Ag2L](PF6)2. In contrast, mixed products (2a + 2b) consisting of 3D networks were obtained from the reaction of L and CuI; 2b linked with a Cu4I4 cubane unit was shown to generate photoluminescence, while 2a linked with a Cu2I2 rhomboid unit does not.