A new series of charge neutral Os(II) isoquinolyl triazolate complexes (1-4) with both trans and cis arrangement of phosphine donors are synthesized, and their structural, electrochemical and photophysical properties are established. In sharp contrast to the cis-arranged complexes 2-4, the trans derivative 1, which shows a planar arrangement of chromophoric N-substituted chelates, offers the most effective extended pi-delocalization and hence the lowest excited state energy gap. These complexes exhibit phosphorescence with peak wavelengths ranging from 692-805 nm in degassed CH2Cl2 at room temperature. Near-infrared (NIR)-emitting electroluminescent devices employing 6 wt % of 1 (or 4) doped in Alq(3) host material are successfully fabricated. The devices incorporating 1 as NIR phosphor exhibit fairly intense emission with a peak wavelength at 814 nm. Forward radiant emittance reaches as high as 65.02 mu W cm(-2), and a peak EQE of similar to 1.5% with devices employing Alq(3), TPBi and/or TAZ as electrontransporting/exciton-blocking layers. Upon switching to phosphor 4, the electroluminescence blue shifts to 718 nm, while the maximum EQE and radiance increase to 2.7% and 93.26 (mu W cm(-2)) respectively. Their performances are optimized upon using TAZ as the electron transporting and exciton-blocking material. The OLEDs characterized represent the only NIR-emitting devices fabricated using charge-neutral and volatile Os(II) phosphors via thermal vacuum deposition.