A series of bis-orthometalated monocyano Ir(III) complexes, [Ir(ppy)(2)PX3CN], (X = Oph, Ph and n-bu) were synthesized and the influence of the steric and electronic effects of the phosphine ligand on the photophysical and electrochemical properties of complexes were studied. These cyano phosphine complexes emit light from an admixture of triplet metal-to-ligand charge-transfer ((MLCT)-M-3) and ligand centered (LC) states in the region of 455-498 nm with a vibronic progression. The trends of the photophysical and electrochemical properties of metal complexes in the series were well understood by the electronic parameter of the phosphine ligands. Polymer light emitting devices were fabricated by doping Ir(ppy)(2)P(n-bu)(3)CN in the PVK host and the device performances were investigated. The maximum external quantum efficiency (eta(ex)) was 1.45% for a 10 wt% Ir(ppy)(2)P(n-bU)(3)CN doped PVK device. A power efficiency of 0.99 lm/W at 230 cd/m(2) and 6 mA/cm(2) was obtained. The corresponding chloro complexes of the general formula [Ir(ppy)(2)PX3Cl] were also synthesized and the optical and device properties were compared with the cyano complexes. (c) 2004 Elsevier B.V. All rights reserved.