The preparation, photophysics, and solid state structures of octahedral organometallic Ir complexes with several different cyclometalated ligands are reported. LrCl3 . nH(2)O cleanly cyclometalates a number of different compounds (i.e., 2-phenylpyridine, 2-(p-tolyl)pyridine, benzoquinoline, 2-phenylbenzothiazole, 2-(1-naphthyl)benzothiazole, and 2-phenylquinoline), forming the corresponding chloride-bridged dimers, C boolean ANDN(2)Ir(mu -Cl)(2)IrC boolean ANDN(2) (C boolean AND Nis a cyclometalated ligand) in good yield. These chloride-bridged dimers react with acetyl acetone (acacH) and other bidentate, monoanionic ligands such as picolinic acid (picH) and N-methylsalicylimine (salH)\ to give monomeric C boolean ANDN(2)Ir(LX) complexes (LX = acac, pie, sal). The emission spectra of these complexes are largely governed by the nature of the cyclometalating ligand, leading to lambda (max) values from 510 to 606 nm for the complexes reported here. The strong spin-orbit coupling of iridium mixes the formally forbidden (MLCT)-M-3 and 3 pi-pi* transitions with the allowed (MLCT)-M-1, leading to a strong phosphorescence with good quantum efficiencies (0.1-0.4) and room temperature lifetimes in the microsecond regime. The emission spectra of the C boolean ANDN(2)Ir(LX) complexes are surprisingly similar to the fac-IrC boolean ANDN(3) complex of the same ligand, even though the structures of the two complexes are markedly different. The crystal structures of two of the C boolean ANDN(2)Ir(acac) complexes (i.e., C boolean ANDN = ppy and tpy) have been determined. Both complexes show cis-C,C', trans-N,N' disposition of the two cyclometalated ligands, similar to the structures reported for other complexes with a "C boolean ANDN(2)Ir" fragment. NMR data (H-1 and C-13) support a similar structure for all of the C boolean ANDN(2)Ir(LX) complexes. Close intermolecular contacts in both (ppy)(2)Ir(acac) and (tpy)(2)Ir(acac) lead to significantly red shifted emission spectra for crystalline samples of the ppy and tpy complexes relative to their solution spectra.