A series of mono-cyclometalated blue phosphorescent indium(III) complexes with two phosphines trans to each other and two cis-ancillary ligands, such as Ir(F(2)Meppy)(PPhMe(2))(2)(H)(Cl). [Ir(F(2)Meppy)(PPhMe(2))(2)(H) (NCMe)](+) and Ir(F(2)Meppy)(PPhMe(2))(2)-(H)(CN), [F(2)Meppy =2-(2',4'-difluorophenyl)-4- methyl-pyridine] were synthesized and studied to tune the phosphorescence wavelength to the deep blue region and to enhance the luminescence efficiencies. We investigate the electron-withdrawing capabilities of ancillary ligands using the DFT and TD-DFT calculations on the ground and excited states of the three complexes to gain insight into the factors responsible for the emission color change and the different luminescence efficiency. Reducing the molecular weight of phosphine ligand with PPhMe(2) leads to a strategy of the efficient deep blue organic light-emitting devices (OLED) by thermal processing instead of the solution processing. The electron-withdrawing difluoro group substituted on the phenyl ring and the cyano strong field ancillary ligand in the trans position to the carbon atom of phenyl ring increased HOMO-LUMO gap and achieved the hypsochromic shift in emission color. As a result, the maximum emission spectra of Ir (F(2)Meppy)(PPhMe(2))(2)(H)(Cl), [Ir(F(2)Meppy)(PPhMe(2))(2)(H)-(NCMe)](+) and Ir(F(2)Meppy)(PPh-Me(2))(2) (H)(CN) were in the ranges of 446, 440, 439 nm, respectively. (C) 2010 Elsevier B.V. All rights reserved.