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

Abstract

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.