title: Efficient Energy Transfer and Metal Coupling in Cyanide-Bridged Heterodinuclear Complexes Based on (Bipyridine)(terpyridine)ruthenium(II) and (Phenylpyridine)iridium(III) Complexes.
abstract: We report a series of cyanide-bridged, heterodinuclear iridium(III)-ruthenium(II) complexes with the generalized formula [Ir((R2)2-ppy)2(CN)(μ-CN)Ru(bpy)(tpy-R1)]PF6 (ppy = 2-phenylpyridine, bpy = 2,2'-bipyridine, and tpy = 2,2':6',2″-terpyridine). The structural, spectroscopic, and electrochemical properties were analyzed in the context of variation of the electron-withdrawing (e.g., -F, -Br, -CHO) and -donating (e.g., -Me) and extended π-conjugated groups at several positions. In total, ten dinuclear complexes and the appropriate model complexes have been prepared. The iridium(III)-based emission is almost fully quenched in these complexes, and only the ruthenium(II)-based emission is observed, which indicates an efficient energy transfer toward the Ru center. Upon oxidation of the Ru center, the fluorinated complexes 2 exhibit a broad intervalence charge-transfer transition in the near-infrared region. The complexes are assigned to a weakly coupled class II system according to the Robin-Day classification. The electronic structure was evaluated by density functional theory (DFT) and time-dependent DFT calculations to corroborate the experimental data.
authors.affiliation: Laboratory of Organic and Macromolecular Chemistry, Friedrich Schiller University Jena , Humboldtstraße 10, 07743 Jena, Germany.|Center for Energy and Environmental Chemistry, Friedrich Schiller University Jena , Philosophenweg 7a, 07743 Jena, Germany.
authors.forename: Kevin
authors.initials: K
authors.lastname: Barthelmes
authors.affiliation: Laboratory of Organic and Macromolecular Chemistry, Friedrich Schiller University Jena , Humboldtstraße 10, 07743 Jena, Germany.|Center for Energy and Environmental Chemistry, Friedrich Schiller University Jena , Philosophenweg 7a, 07743 Jena, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Jäger
authors.affiliation: Leibniz Institute of Photonic Technology , Albert-Einstein-Straße 9, 07745 Jena, Germany.|Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich Schiller University Jena , Helmholtzweg 4, 07743 Jena, Germany.
authors.forename: Joachim
authors.initials: J
authors.lastname: Kübel
authors.affiliation: Laboratory of Organic and Macromolecular Chemistry, Friedrich Schiller University Jena , Humboldtstraße 10, 07743 Jena, Germany.|Center for Energy and Environmental Chemistry, Friedrich Schiller University Jena , Philosophenweg 7a, 07743 Jena, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Friebe
authors.affiliation: Laboratory of Organic and Macromolecular Chemistry, Friedrich Schiller University Jena , Humboldtstraße 10, 07743 Jena, Germany.|Center for Energy and Environmental Chemistry, Friedrich Schiller University Jena , Philosophenweg 7a, 07743 Jena, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Winter
authors.affiliation: Leibniz Institute of Photonic Technology , Albert-Einstein-Straße 9, 07745 Jena, Germany.
authors.forename: Maria
authors.initials: M
authors.lastname: Wächtler
authors.affiliation: Center for Energy and Environmental Chemistry, Friedrich Schiller University Jena , Philosophenweg 7a, 07743 Jena, Germany.|Leibniz Institute of Photonic Technology , Albert-Einstein-Straße 9, 07745 Jena, Germany.|Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich Schiller University Jena , Helmholtzweg 4, 07743 Jena, Germany.
authors.forename: Benjamin
authors.initials: B
authors.lastname: Dietzek
authors.affiliation: Laboratory of Organic and Macromolecular Chemistry, Friedrich Schiller University Jena , Humboldtstraße 10, 07743 Jena, Germany.|Center for Energy and Environmental Chemistry, Friedrich Schiller University Jena , Philosophenweg 7a, 07743 Jena, Germany.
authors.forename: Ulrich S
authors.initials: US
authors.lastname: Schubert