The azide anion is widely used as a ligand in coordination chemistry. Despite its ubiquitous presence, controlled synthesis of azido complexes remains a challenging task. Making use of click-derived tripodal ligands, we present here various coordination motifs of the azido ligands, the formation of which appears to be controlled by the peripheral substituents on the tripodal ligands with otherwise identical structure of the coordination moieties. Thus, the flexible benzyl substituents on the tripodal ligand TBTA led to the formation of the first example of an unsupported and solely ptixazido-bridged dicobalt(II) complex. The more rigid phenyl substituents on the TPTA ligand deliver an unsupported and solely mu(1,3),-azido-bridged dicobalt(II) complex. Bulky diisopropylphenyl substituents on the TDTA ligand deliver a doubly mu(1,1),-azido-bridged dicobalt(II) complex. Intriguingly, the mononuclear copper(II) complex [Cu(TBTA)N-3](+) is an excellent synthon for generating mixed dinuclear complexes of the form [(TBTA)Co(mu(1,1)-N-3)Cu(TBTA)](3+) or [(TBTA)Cu(mu(1,1)-N-3)Cu(TPTA)](3+), both of which contain a single unsupported mu(1,1)-N-3 as a bridge. To the best of our knowledge, these are also the first examples of mixed dinuclear complexes with a monoazido bridge. All complexes were crystallographically characterized, and selected examples were probed-via magnetometry and high-field EPR spectroscopy to elucidate the electronic structures of these complexes and the nature of magnetic coupling in the various azido-bridged complexes. These results thus prove the power of click-tripodal ligands in generating hitherto unknown chemical structures and properties.