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.

2 (μ-tape)](ClO 4 ) 4 · MeCN were determined. The UV/Vis absorption spectra of [1](PF 6 ) 2 , [2](PF 6 ) 2 , and [3](PF 6 ) 4 in acetonitrile display intense low-energy d π (Ru)Ǟπ* (dape or tape) MLCT absorption bands centered at 579, 637, and 794 nm, respectively. Reversible metal oxidations for the bimetallic complex [{Ru(L-N 4 Me 2 )} 2 (μ-tape)] 4+ ([3] 4+ ) are detected at 1.69 and [a]

A simple and straightforward approach to new polymetallic AgI and CuI supramolecules is presented. The reaction of N,P,N,P,N ligand 2 with AgI ions affords a trimetallic complex bearing a triangular Ag3 core; metallophilic interactions are stabilized by ligands that display a multiple bridging coordination mode as 10‐electron donors. Heteroleptic polymetallic AgI and CuI complexes based on ligand 2 and the 1,12‐diazaperylene (dape) ligand are obtained by an alternative molecular organization of the polymetallic arrays compared to that in homoleptic complexes of ligand 2.

In the title compound, rac-[Ru(C14H16N2)2(C16H8N4)](PF6)2·3C2H3N, discrete dimers of complex cations, [Ru(tmbpy)2­tape]2+, of opposite chirality are formed (tmbpy = tetra­methyl­bipyridine; tape = tetraazaperylene), held together by π–π stacking inter­actions between the tetra­aza­perylene moieties with centroid–centroid distances in the range 3.563 (3)–3.837 (3) Å. These inter­actions exhibit a parallel displaced π–π stacking mode. Additional weak C—H⋯π-ring and C—H⋯N and C—H⋯F inter­actions are found, leading to a three-dimensional architecture. The RuII atom is coordinated in a distorted octa­hedral geometry. The counter-charge is provided by two hexa­fluorido­phosphate anions and the asymmetric unit is completed by three aceto­nitrile solvent mol­ecules of crystallization. Four F atoms of one PF6 − anion are disordered over three sets of sites with occupancies of 0.517 (3):0.244 (3):0.239 (3). Two aceto­nitrile solvent mol­ecules are highly disordered and their estimated scattering contribution was subtracted from the observed diffraction data using the SQUEEZE option in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148–155].

The highlighted ruthenium complex forms discrete dimers by π–π stacking inter­actions and hydrogen bonds. This combination of inter­actions results in an unusual nearly face-to-face π–π stacking mode.