Two methods of post-synthetic modification (Suzuki coupling and CuAAC click-reaction) were applied to Ir(iii) complexes [Ir(C^N)2N^N]+ to provide the second highly selective donor site. One family of functionalized complexes was used to demonstrate the potential of post-synthetic modification for controlled construction of d–d and d–f binuclear complexes. The complexes obtained were characterized by CHN elemental analysis{,} NMR spectroscopy{,} ESI mass-spectrometry{,} FTIR spectroscopy and single crystal X-ray diffraction analysis. By means of XPS and NEXAFS spectroscopy the coordination of diimine donor site to the Ln(iii) centre has been definitely confirmed. The photophysical properties of mono- and binuclear complexes were carefully investigated{,} and the evolution of luminescent characteristics during the formation of a system of connected metallocenters is also discussed. TDDFT calculations were used to describe the luminescence mechanism and to confirm the conclusions made on the basis of experimental data.