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A series of novel regioselective substituted tpphz ligands and two novel mononuclear ruthenium complexes of the type [(tbbpy)2Ru(tpphzRn)](PF6)2 (where tbbpy = 4,4′-di-tert.-butyl-2,2′-bipyridine, tpphz = tetrapyrido[3,2-a:2′,3′-c:3′′,2′′-h:2′′′,3′′′-j]phenazine, with n = 2 and R represents the bromine substituents at different positions) have been synthesized. All compounds were completely characterized by NMR and MS spectroscopy, absorption and steady-state emission spectroscopy as well as emission lifetime and electrochemical measurements. Additionally the solid-state structures of the two isomers [(tbbpy)2Ru(Br2tpphz)](PF6)26 and [(tbbpy)2Ru(tpphzBr2)](PF6)27 are presented and compared with the results of density-functional theory calculations (DFT). Furthermore calculated Raman spectra were obtained by means of DFT calculations and used to assign the vibrational modes of the measured off resonance Raman spectra. A clear influence caused by the electronic effects of the different type and position of the substituents of tpphz on the photophysical behavior was observed