A novel compound containing both a 2,2-bipyridine as well as a 2-ureido-4[1H]-ureidopyrimidinone supramolecular moiety ( 3) has been synthesised and fully characterized by 1H-NMR, MALDI-TOFMS, UV-vis and IR spectroscopy. Subsequent coordination to iridium and ruthenium polypyridyl precursors allowed the formation of iridium(III) and ruthenium(II) polypyridyl dimers ( 5 and 7) assembled via quadruple hydrogen-bonding as well as metal coordination interactions. The syntheses and complete characterization of these materials by means of two-dimensional NMR techniques (1H–1H COSY and 1H–1H DOSY) as well as IR and MALDI-TOFMS are described in detail. Comparative studies of the optical properties of the luminescent model complexes ( 5 and 7) and the dimer species ( 5 and 7) are also illustrated. In addition, good processability of the materials has been demonstrated by inkjet printing leading to thin films revealing their potential for light-emitting devices.