Anion-Templated Self-Assembly of Silver(I) Frameworks Bridged by μ-, μ₃-, μ₄-1,2,4,5-Tetrazine

The formation of Ag(I)-1,2,4,5-tetrazines(ttz) based coordination polymers via the Ag−N coordination and anion−π interactions is described. Coordination-driven self-assembly is a key step to construct coordination polymers, and ttz, an electron-deficient aromatic ring compound, forms interesting anion−π interactions. In this study, a series of silver salts, AgX [X = BF₄, PF₆ and CF₃SO₃ (OTf)], is introduced to determine the influence of shape and size of anions on the formation of coordination polymers, {[Ag(ttz)](BF₄)}_n (1), {[Ag₂(ttz)₃](PF₆)₂}_n (2) and {[Ag₂(ttz)₃(OTf)](OTf)}_n (3). It shows different types of channels in polymers and the coordination modes of ttz (μ, μ₃, and μ₄). The structure of coordination polymers and the influence of anion−π interactions are revealed by single crystal X-ray diffraction. In particular, 3 shows not only the anion−π interaction but also the coordination between the anion and Ag(I) which contributes to the unique framework compared to 1 and 2.