Synthetic control of the mutual arrangement of the cyclometalated ligands (C boolean AND N) in Ir(III) dimers, [Ir(C boolean AND N)(2)Cl](2), and cationic bis-cyclometalated Ir(III) complexes, [Ir(C boolean AND N)(2)-(L boolean AND L)](+) (L boolean AND L = neutral ligand), is described for the first time. Using I-benzy1-4-(2,4-difluorophenyl)-1H-1,2,3-triazole (HdfptrBz) as a cyclometalating ligand, two different Ir(III) dimers, [Ir(dfptrBz)(2)Cl](2), are synthesized depending on the reaction conditions. At 80 degrees C, the dimer with an unusual mutual cis-C,C and cis-N,N configuration of the C boolean AND N ligands is isolated. In contrast, at higher temperature (140 degrees C), the geometrical isomer with the common cis-C,C and trans-N,N arrangement of the C boolean AND N ligand is obtained. In both cases, an asymmetric bridge, formed by a chloro ligand and two adjacent nitrogens of the triazole ring of one of the cyclometalated ligands, is observed. The dimers are cleaved in coordinating solvents to give the solvent complexes [Ir(dfptrBz)(2)Cl(S)] (S = DMSO or acetonitrile), which maintain the C boolean AND N arrangement of the parent dimers. Controlling the C boolean AND N ligand arrangement in the dimers allows for the preparation of the first example of geometrical isomers of a cationic bis-cyclometalated Ir(III) complex. Thus, N,N-trans-[Ir-(dfptrBz)(2)(dmbpy)](+) (dmbpy = 4,4'-dimethyl-2,2'-bipyridine), with cis-C,C and trans-N,N arrangement of the C boolean AND N ligands, as well as N,N-cis-[Ir(dfptrBz)(2)(dmbpy)](+), with cis-C,C and cis-N,N C boolean AND N ligand orientation, are synthesized and characterized. Interestingly, both isomers show significantly different photophysical and electroluminescent properties, depending on the mutual arrangement of the C boolean AND N ligands. Furthermore, quantum chemical calculations give insight into the observed photophysical experimental data.