The novel terthiophene (3T) oligomer 6 and a series of cationic Ir(III) bis-cyclometalates [Ir(C boolean AND N)(2)(N boolean AND N)]PF6 9-12 were prepared. The synthesis, characterization, electrochemical, and photophysical properties are reported. The cyclometalating ligands (C boolean AND N) are 2-phenylpyridinato (ppy) or the 3T oligomer (3T-ppy), asymmetrically capped in the 5 and 5 '' positions with the ppy and mesityl groups. The diimine ligands (N boolean AND N) are 2,2'-bipyridine (bpy) or 4-NO2-bipyridine (4-NO2-bpy). Hybrid metal-organic complexes 11 and 12 bear 3T-pendants ligated through the ppy cap, 10 and 12 contain NO2 functionalized diimines, whereas 9 contains neither. Structural characterization of 10 by single crystal X-ray diffraction confirms the presence of the NO2 substituent and pseudo-octahedral coordination geometry about the Ir(III) ion. Cyclic voltammetry highlights the large electron withdrawing effect of the NO2 substituent, providing an 850 mV shift toward lower potentials for the first diimine centered reduction of 10 and 12. Strong overlap of the intense pi -> pi* absorptions of the 3T-pendants with Ir(III) charge transfer bands is evident in complexes of 11 and 12, precluding the possibility for selective excitation of either chromophore. Photoexcitation (lambda(ex) = 400 nm) of the series affords strong luminescence from the 3T oligomer 6 and the unsubstituted 9, with phi(em) = 0.11. In stark contrast the NO2 and 3T functionalized complexes 10-12 display near total quenching of luminescence. Computations of the ground and excited state electronic structure using density functional theory (DFT) and time-dependent DFT (TD-DFT) indicate that both the NO2 and 3T substituents play an important role in excited state deactivation of complexes 10-12. A substantial electronic contribution of the NO2 substituent results in stabilization of the diimine based molecular orbital (MO) and offers an efficient nonradiative decay pathway for the excited state. Spin-orbit coupling effects of the Ir(III) ion lead to efficient population of the low lying, nonluminescent, triplet states centered on the 3T-pendants.