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)](PF(6))(2), [1](PF(6))(2)-[5](PF(6))(2), and [{Ru(L-L)(2)}(2)(μ-tape)](PF(6))(4), [6](PF(6))(4)-[10](PF(6))(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·2CHCl(3) and the mononuclear complexes [Ru(bpy)(2)(tape)](PF(6))(2)·0.5CH(3)CN·0.5toluene, [Ru(dmbpy)(2)(tape)](PF(6))(2)·2toluene and [Ru(dtbbpy)(2)(tape)](PF(6))(2)·3acetone·0.5H(2)O 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.

Mono‐ and Dinuclear Ruthenium(II)–1,6,7,12‐Tetraazaperylene Complexes of N,N′‐Dimethyl‐2,11‐diaza[3.3](2,6)‐pyridinophane

“…The potential difference ΔE = 410 mV and the intervalence-charge-transfer (IVCT) transition at 2472 nm indicate a high degree of electronic interaction between the two ruthenium ions mediated through the tape bridging ligand. Monoreduced species [1] + , [2] + , and [3] 3+ yield EPR signals indicating that the unpaired electron is mainly centered on the "large surface" ligands dape or tape. The second reduction in each complex and the second oxidation in [3] 4+ prove to be irreversible in these spectroelectrochemical experiments.…”

“…The second reduction in each complex and the second oxidation in [3] 4+ prove to be irreversible in these spectroelectrochemical experiments. [2] Both dinuclear complexes [{Ru(bpy) 2 } 2 (μ-BL)] 4+ (BL = dbneil, [5] tape [2] ) exhibit two well-resolved reversible metal-centered oxidations in their cyclic voltammograms, indicating significant metal-metal interactions mediated by the conjugated bridging ligands. characterized by spectroelectrochemical methods.…”

“…Monoreduced species [1] + , [2] + , and [3] 3+ yield EPR signals indicating that the unpaired electron is mainly centered on the "large surface" ligands dape or tape. [2,5] The ligand tape can be synthesized in gram quantities and is sufficiently soluble in alcohol solvents to be used in the preparation of metal complexes. [6] Recently, we synthesized the corresponding mono-and dinuclear ruthenium(II) complexes [Ru(bpy) 2 (tape)] 2+ and [{Ru(bpy) 2 } 2 (μ-tape)] 4+ with the potentially bridging ligand tape.…”

“…characterized by spectroelectrochemical methods. [2] Both diimine chelate units of tape are able to coordinate ruthenium(II) ions under relatively mild reaction conditions. [2] Both dinuclear complexes [{Ru(bpy) 2 } 2 (μ-BL)] 4+ (BL = dbneil, [5] tape [2] ) exhibit two well-resolved reversible metal-centered oxidations in their cyclic voltammograms, indicating significant metal-metal interactions mediated by the conjugated bridging ligands.…”

Forces from periodic charging of adsorbed molecules

“…66, it was reported that 1,6,7,12-tetraazaperylene (TAPE) 69 molecules at the edges of self-assembled islands grown on Ag(111) can be deliberately switched in their charge state with the electric field from a scanning-probe tip. The selfassembled islands formed at room temperature have a periodic structure, in which each molecule is rotated by roughly Θ = 80 • with respect to its four neighbors.…”