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 and fluorescence properties and the possibilities of functionalization in the 3 and 6 positions allowing 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 their solid state structures and physical properties. After a description of the most representative complexes containing unsubstituted TTZ as a ligand, symmetric TTZ ligands and complexes derived thereof are discussed in the order: 3,6-bis(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(monopicolylamine)-tetrazine, 3,6-bis(vanillin-hydrazinyl)-tetrazine and TTZ containing carboxylic acids. Remarkable results have been obtained in recent years for metal-organic frameworks and magnetic compounds in which magnetic coupling is enhanced when the tetrazine bridge is reduced to radical anions. 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.