Dokument-ID Dokumenttyp Verfasser/Autoren Herausgeber Haupttitel Abstract Auflage Verlagsort Verlag Erscheinungsjahr Seitenzahl Schriftenreihe Titel Schriftenreihe Bandzahl ISBN Quelle der Hochschulschrift Konferenzname Quelle:Titel Quelle:Jahrgang Quelle:Heftnummer Quelle:Erste Seite Quelle:Letzte Seite URN DOI Abteilungen OPUS4-45884 Wissenschaftlicher Artikel Brietzke, Thomas Martin; Kelling, Alexandra; Schilde, Uwe; Mickler, Wulfhard; Holdt, Hans-Jürgen Heterodinuclear Ruthenium(II) Complexes of the Bridging Ligand 1,6,7,12-Tetraazaperylene with Iron(II), Cobalt(II), Nickel(II), as well as Palladium(II) and Platinum(II) The first heterodinuclear ruthenium(II) complexes of the 1,6,7,12-tetraazaperylene (tape) bridging ligand with iron(II), cobalt(II), and nickel(II) were synthesized and characterized. The metal coordination sphere in this complexes is filled by the tetradentate N,N-dimethyl-2,11-diaza[3.3](2,6)-pyridinophane (L-N4Me2) ligand, yielding complexes of the general formula [(L-N4Me2)Ru(mu-tape)M(L-N4Me2)](ClO4)(2)(PF6)(2) with M = Fe {[2](ClO4)(2)(PF6)(2)}, Co {[3](ClO4)(2)(PF6)(2)}, and Ni {[4](ClO4)(2)(PF6)(2)}. Furthermore, the heterodinuclear tape ruthenium(II) complexes with palladium(II)- and platinum(II)-dichloride [(bpy)(2)Ru(-tape)PdCl2](PF6)(2) {[5](PF6)(2)} and [(dmbpy)(2)Ru(-tape)PtCl2](PF6)(2) {[6](PF6)(2)}, respectively were also prepared. The molecular structures of the complex cations [2](4+) and [4](4+) were discussed on the basis of the X-ray structures of [2](ClO4)(4)MeCN and [4](ClO4)(4)MeCN. The electrochemical behavior and the UV/Vis absorption spectra of the heterodinuclear tape ruthenium(II) complexes were explored and compared with the data of the analogous mono- and homodinuclear ruthenium(II) complexes of the tape bridging ligand. Weinheim Wiley-VCH 2016 6 Zeitschrift für anorganische und allgemeine Chemie 642 8 13 10.1002/zaac.201500645 Institut für Chemie OPUS4-35592 Wissenschaftlicher Artikel Brietzke, Thomas Martin; Mickler, Wulfhard; Kelling, Alexandra; Schilde, Uwe; Krüger, Hans-Joerg; Holdt, Hans-Jürgen Mono- and dinuclear Ruthenium(II)-1,6,7,12-Tetraazaperylene complexes of N,N '-Dimethyl-2,11-diaza[3.3](2,6)-pyridinophane Ruthenium(II) complexes [Ru(L-N4Me2)(dape)](PF6)2 {[1](PF6)2}, [Ru(L-N4Me2)(tape)](PF6)2 {[2](PF6)2}, and [{Ru(L-N4Me2)}2(mu-tape)](PF6)4 {[3](PF6)4} were synthesized in two reaction steps by first reacting [Ru(DMSO)4Cl2] with tetraazamacrocyclic ligand N,N'-dimethyl-2,11-diaza[3.3](2,6)-pyridinophane (L-N4Me2) in ethanol under microwave irradiation to the intermediate [Ru(L-N4Me2)Cl2], which was subsequently, without further isolation, reacted with 1,12-diazaperylene (dape) or 1,6,7,12-tetraazaperylene (tape). X-ray structures of [Ru(L-N4Me2)(dape)](PF6)2, [Ru(L-N4Me2)(tape)](PF6)2.acetone, and [{Ru(L-N4Me2)}2(mu-tape)](ClO4)4.MeCN were determined. The UV/Vis absorption spectra of [1](PF6)2, [2](PF6)2, and [3](PF6)4 in acetonitrile display intense low-energy dp(Ru)?p* (dape or tape) MLCT absorption bands centered at 579, 637, and 794 nm, respectively. Reversible metal oxidations for the bimetallic complex [{Ru(L-N4Me2)}2(mu-tape)]4+ ([3]4+) are detected at 1.69 and 1.28 V vs. SCE. The potential difference ?E = 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. All three complexes, [1]2+, [2]2+, and [3]4+, were characterized by UV/Vis spectroelectrochemistry. The monooxidized and monoreduced states, [1]3+, [2]3+, [3]5+, and [1]+, [2]+, [3]3+, are accessible by reversible one-electron oxidation and one-electron reduction processes, respectively, as documented by the observation of several stable isosbestic points in the spectral progressions. The second reduction in each complex and the second oxidation in [3]4+ prove to be irreversible in these spectroelectrochemical experiments. 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. Weinheim Wiley-VCH 2012 12 European journal of inorganic chemistry : a journal of ChemPubSoc Europe 29 4632 4643 10.1002/ejic.201200667 Institut für Chemie