Mono- and dinuclear ruthenium(ii) 1,6,7,12-tetraazaperylene complexes

Abstract

We report the synthesis of free 1,6,7,12-tetraazaperylene (tape). Tape was obtained from 1,1′-bis-2,7-naphthyridine by potassium promoted cyclization followed by oxidation with air. Mono- and dinuclear ruthenium(II) 1,6,7,12-tetraazaperylene complexes of the general formulas [Ru(L–L)₂(tape)](PF₆)₂, [1](PF₆)₂–[5](PF₆)₂, and [{Ru(L–L)₂}₂(μ-tape)](PF₆)₄, [6](PF₆)₄–[10](PF₆)₄, with{L–L = phen, bpy, dmbpy (4,4′-dimethyl-2,2′-bipyridine), dtbbpy (4,4′-ditertbutyl-2,2′-bipyridine) and tmbpy (4,4′5,5′-tetramethyl-2,2′-bipyridine)}, respectively, were synthesized. The X-ray structures of tape·2CHCl₃ and the mononuclear complexes [Ru(bpy)₂(tape)](PF₆)₂·0.5CH₃CN·0.5toluene, [Ru(dmbpy)₂(tape)](PF₆)₂·2toluene and [Ru(dtbbpy)₂(tape)](PF₆)₂·3acetone·0.5H₂O were solved. The UV-vis absorption spectra and the electrochemical behavior of the ruthenium(II) tape complexes were explored and compared with the data of the analogous dibenzoeilatin (dbneil), 2,2′-bipyrimidine (bpym) and tetrapyrido[3,2-a:2′,3′-c:3′′,2′′-h:2′′′,3′′′-j]phenazin (tpphz) species.