title: Synthesis and characterization of regioselective substituted tetrapyridophenazine ligands and their Ru(II) complexes.
abstract: A series of novel regioselective substituted tpphz ligands and two novel mononuclear ruthenium complexes of the type [(tbbpy)(2)Ru(tpphzR(n))](PF(6))(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)(2)Ru(Br(2)tpphz)](PF(6))(2) 6 and [(tbbpy)(2)Ru(tpphzBr(2))](PF(6))(2) 7 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.
authors.affiliation: Institute of Inorganic and Analytical Chemistry, Friedrich-Schiller-University Jena, August-Bebel-Strasse 2, 07743, Jena, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Karnahl
authors.forename: Stefanie
authors.initials: S
authors.lastname: Tschierlei
authors.forename: Christian
authors.initials: C
authors.lastname: Kuhnt
authors.forename: Benjamin
authors.initials: B
authors.lastname: Dietzek
authors.forename: Michael
authors.initials: M
authors.lastname: Schmitt
authors.forename: Jürgen
authors.initials: J
authors.lastname: Popp
authors.forename: Matthias
authors.initials: M
authors.lastname: Schwalbe
authors.forename: Sven
authors.initials: S
authors.lastname: Krieck
authors.forename: Helmar
authors.initials: H
authors.lastname: Görls
authors.forename: Frank W
authors.initials: FW
authors.lastname: Heinemann
authors.forename: Sven
authors.initials: S
authors.lastname: Rau
mesh_terms: D018360:Crystallography, X-Ray; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010619:Phenazines / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D010619:Phenazines; D012428:Ruthenium