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.