We describe the synthesis and the structural characterization of new H₂L(CF₃CO₂)₂ (1) and H₂L(Ph₂PO₄)₂ (2) compounds containing the diprotonated form (H₂L2+) of the tetrazine-based molecule 3,6-di(pyridin-4-yl)-1,2,4,5-tetrazine. X-ray diffraction (XRD) analysis of single crystals of these compounds showed that H₂L2+ displays similar binding properties toward both anions when salt bridge interactions are taken into account. Nevertheless, the different shapes, sizes and functionalities of trifluoroacetate and diphenyl phosphate anions define quite different organization patterns leading to the peculiar crystal lattices of 1 and 2. These three-dimensional (3D) architectures are self-assembled by a variety of non-covalent forces, among which prominent roles are played by fluorine-π (in 1) and anion-π (in 2) interactions.
Keywords: anion complexes; anion–π; crystal structures; halogen–π; tetrazines; weak forces.