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The interest in Cr(III) complexes has been renewed over the past decades for building practical guidelines in the design of efficient earth-abundant phosphorescent near-infrared emitters. In that context, we report the first family of homoleptic tri(didentate) Cr(III) complexes [Cr L 3 ] 3+ based on polyaromatic ligands inducing 6-membered chelate rings, namely, the bis(1-methylimidazol-2-yl)ketone ( L = bim), and bis(1-methylimidazol-2-yl)ethane ( L = bie) ligands. The programmed close-to-perfect octahedral microsymmetry of {Cr L = bie) ligands. The programmed close-to-perfect octahedral microsymmetry of {Cr III N 6 } chromophores found in [Cr(bik) 3 ](OTf) 3 ( 1 ), [Cr(bim) 3 ](OTf) 3 ), and [Cr(bie) 2 ), and [Cr(bie) 3 ](BF 4 ) 3 ) ensures a ligand-field strength large enough to induce intense and long-lived Cr-based phosphorescence. Impressive excited-state lifetimes (5.0-8.2 ms) were obtained at low temperatures for the [Cr( 3 ) ensures a ligand-field strength large enough to induce intense and long-lived Cr-based phosphorescence. Impressive excited-state lifetimes (5.0-8.2 ms) were obtained at low temperatures for the [Cr( L ) 3 ] 3+ in deaerated solutions. Moreover, the photophysical features of the three homoleptic complexes are barely influenced by the presence of dioxygen presumably because of the poor overlap between the Cr-based phosphorescence spectra (ca. 14100 cm 1 ) and the -1 ) and the 1 Σ g + transition in the absorption spectrum of dioxygen (13100 cm 3 ). The multiredox electrochemical pattern of g is evidenced by cyclic voltammetry as well as its strong photooxidant behavior. The pH sensitivity of - and -1 luminescence is discussed, along with the reactivity of their β-diketiminate derivatives.1 is evidenced by cyclic voltammetry as well as its strong photooxidant behavior. The pH sensitivity of 2 and 3 luminescence is discussed, along with the reactivity of their β-diketiminate derivatives.