Ru–dppz (dppz = dipyrido[3,2-a:2′,3,3′-c]phenazine) complexes play an important role as environmentally sensitive luminescence sensors and building blocks for larger supramolecular compounds. Their photophysical properties are known to be highly sensitive to intermolecular solvent–solute interactions and solvent bulk-properties. Here, the synthesis and characterisation of a novel Ru–dppz derivative is reported. The potential of drastically tuning the photophysical properties of such complexes is exemplified, by introducing very simple structural modifications, namely bromine, into the dppz-ligand scaffold. The photophysics i.e. nature of excited states and the excited-state relaxation pathway of the various complexes has been investigated by means of electrochemical measurements, steady-state emission experiments and femtosecond time-resolved spectroscopy. It could be shown that the location of bromine substitution influences the relative energy between a luminescent and a non-luminescent metal-to-ligand charge-transfer state and therefore quenches or facilitates transitions between both. Hence it is illustrated that the luminescent properties and the underlying ultrafast excited-state dynamics of the complexes can be controlled by structural variations, i.e. by intramolecular interactions as opposed to changes in the intermolecular interactions.