A series of monoanionic Ir(III) complexes (24) of general formula [Ir(C boolean AND N)2(b-trz)](TBA) are presented, where C boolean AND N indicates three different cyclometallating ligands (Hppy = 2-phenylpyridine; Hdfppy = 2-(2,4-difluoro-phenyl)pyridine; Hpqu = 2-methyl-3-phenylquinoxaline), b-trz is a bis-tetrazolate anionic N boolean AND N chelator (H(2)b-trz = di(1H-tetrazol-5-yl)methane), and TBA = tetrabutylammonium. 24 are prepared in good yields by means of the reaction of the suitable b-trz bidentate ligand with the desired iridium(III) precursor. The chelating nature of the ancillary ligand, thanks to an optimized structure and geometry, improves the stability of the complexes, which have been fully characterized by NMR spectroscopy and high-resolution MS, while X-ray structure determination confirmed the binding mode of the b-trz ligand. Density functional theory calculations show that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are mainly localized on the metal center and the cyclometalating ligands, while the bis-tetrazolate unit does not contribute to the frontier orbitals. By comparison with selected classes of previously published cationic and anionic complexes with high ligand field and even identical cyclometallating moieties, it is shown that the HOMOLUMO gap is similar, but the absolute energy of the frontier orbitals is remarkably higher for anionic vs cationic compounds, due to electrostatic effects. 24 exhibit reversible oxidation and reduction processes, which make them interesting candidates as active materials for light emitting electrochemical cells, along with red, green, and blue emission, thanks to the design of the C boolean AND N ligands. Photoluminescence quantum yields range from 28% (4, C boolean AND N = pqu, red emitter) to 83% (3, C boolean AND N = dfppy, blue emitter) in acetonitrile, with the latter compound reaching 95% in poly(methyl methacrylate) (PMMA) matrix. In thin films, the photoluminescence quantum yield decreases substantially probably due to the small intersite distance between the complexes and the presence of quenching sites. In spite of this, surprisingly stable electroluminescence was observed for devices employing complex 2, demonstrating the robustness of the anionic compounds.