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 = BF 4 , PF 6 and CF 3 SO 3 (OTf)], is introduced to determine the influence of shape and size of anions on the formation of coordination polymers, {[Ag(ttz)](BF 4 )} n ( 1 ), {[Ag 2 (ttz) 3 ](PF 6 ) 2 } n ( 2 ) and {[Ag 2 (ttz) 3 (OTf)](OTf)} n ( 3 ). It shows different types of channels in polymers and the coordination modes of ttz (μ, μ 3 , and μ 4 ). 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 .