One of the most intriguing nitrogen based aromatic heterocycles is 1,2,4,5-tetrazine or s-tetrazine (TTZ) thanks to its electron acceptor character, fluorescent properties and possibilities of functionalization in the 3,6 positions allowing the access to various ligands. In this Review we focus on the two main families of TTZ based ligands, i.e. ditopic symmetric and monotopic non-symmetric, together with their metal complexes, with a special emphasis on the solid state structures and physical properties. After a description of the most representative complexes containing the unsubstituted TTZ as ligand, the symmetric TTZ ligands and complexes derived thereof are discussed in the order: 3,6bis(2-pyridyl)-tetrazine, 3,6-bis(3-pyridyl)-tetrazine, 3,6-bis(4-pyridyl)-tetrazine, 3,6-bis(2-pyrimidyl)tetrazine, 3,6-bis(2-pyrazinyl)-tetrazine, 3,6-bis(monopicolyamine)-tetrazine, 3,6-bis(vanillinhydrazinyl)-tetrazine and TTZ containing carboxylic acids. Remarkable results have been obtained in the recent years in metal-organic frameworks and magnetic compounds in which the magnetic coupling is enhanced when the tetrazine bridge is reduced in radical anion. The non-symmetric ligands, such as dipicolylamine-TTZ and monopicolylamine-TTZ, are comparatively more recent than the symmetric ones. They allow in principle the preparation of mononuclear complexes in a controlled manner, although binuclear complexes have been isolated as well. Moreover, in the monopicolylamine-TTZ-Cl ligand, deprotonation of the amine, thanks to the electron acceptor character of TTZ, afforded a negatively charged ligand equivalent of a guanidinate.