This article demonstrates a series of cyclometalated Ir(III) complexes of the type [Ir-III(C<^>N)2(N<^>N)]-(PF6), where C<^>N is 2-phenylpyridine, and N<^>N corresponds to the 4,4'-pi-conjugated 2,2'-bipyridine ancillary ligands. All these compounds were synthesized through splitting of the binuclear dichloro-bridged complex precursor, [Ir(C<^>N)(2)(mu-Cl)](2), with the appropriate bipyridine ligands followed by the anion exchange reaction. The linear and nonlinear absorption properties of the synthesized complexes were investigated. The absorption spectra of all the title complexes exhibit a broad structureless feature in the spectral region of 350-700 nm with two bands being well-resolved in most of the cases. The structures of all the compounds were modeled in dichloromethane using the density functional theory (DFT) algorithm. The nature of electronic transitions was further comprehended on the basis of time dependent DFT analysis, which indicates that the origins of various bands are primarily due to intraligand charge transfer transitions along with mixed-metal and ligand-centered transitions. The synthesized compounds are found to be nonemissive at room temperature because of probable nonradiative deactivation pathways of the T-1 state that compete with the radiative (phosphorescence) decay modes. However, the frozen solutions of compounds Ir(MS 3) and Ir(MS 5) phosphoresce at the near-IR region, the other complexes remaining nonemissive up to 800 nm wavelength window. The two-photon absorption studies on the synthesized complexes reveal that values of the absorption cross-section are quite notable and lie in the range of 300-1000 GM in the picosecond case and 45-186 GM in the femtosecond case.