Two new cyclometalated Rh(III) and Ir(III) complexes-have been synthesized, and their absorption spectra, luminescence properties (in rigid matrix at 77 K and in fluid solution at room temperature), and electrochemical behavior have been investigated and compared to those of other similar Rh(III) and Ir(III) cyclometalated species. The new compounds are [Rh(ppy)(2)(dpt-NH2)](PF6) (1) and [Ir(ppy)(2)(dpt-NH2)](PF6) (2) (ppy = phenylpyridine anion; dpt-NH2 = 4-amino-3,5-bis(2-pyridyl)-4H-1,2,4-triazole). The absorption spectra of the compounds are dominated by intense ligand-centered bands in the UV region(epsilon(max) in the range 10(4)-10(5) M(-1) cm(-1)) and by moderately intense metal-to-ligand charge transfer bands-in the visible region (epsilon(max) in the range 10(3)-10(5) M(-1) cm(-1)). A reversible oxidation occurs for 2 at +1.23 V vs SCE, assigned removal of an electron from a metal-centered d pi orbital, while an irreversible oxidation is observed for 1 at more positive potentials (E(peak) = +1.51 V vs SCE), assigned to removal of an electron from a metal-ligand (C-) sigma-bonding orbital. Both complexes are luminescent in rigid matrices at 77 K (1, lambda(max) = 458 nm, tau = 160 mu s; 2, lambda(max) = 475 nm; tau = 5.8 mu s), while only the Ir compound emits in fluid solution at room temperature (lambda(max) = 560 nm, tau = 870 ns, Phi = 0.246). The emission originates from a metal-perturbed, triplet ppy-centered excited state for the Rh species while a triplet MLCT level is responsible for the emission of the Ir compound. The results obtained are a step toward the preparation of photoactive and redox-active multinuclear compounds based on bis(pyridyl)triazole derivative bridges and incorporating Ir(III) and Rh(III) cyclometalated building blacks.