New cationic metallo ligands L1-L3 based on bis(terpyridine) ruthenium(II) complexes decorated with differently substituted 2,2'-bipyridines attached via amide groups (5-NHCO-bpy, 4-CONH-bpy, 5-CONH-bpy) were prepared. Coordination of Re(I)Cl(CO)(3) fragments to the bpy unit gives the corresponding bimetallic Ru~Re complexes 1-3. Hydrogen bonds of the bridging amide groups to [PF(6)](-) counterions or to water molecules are observed both in the solid state and in solution. The impact of the amide orientation, the connecting site, and the coordination of counterions on redox and photophysical properties is explored. Both the metallo ligands L1-L3 and the bimetallic complexes 1-3 are emissive at room temperature in fluid solution. The emission originates from (3)MLCT(Ru) states in all cases. Accordingly, the first oxidation of L1-L3 and 1-3 to [L1](+)-[L3](+) and [1](+)-[3](+) is assigned to the Ru(II/III) couple, while the first reduction to [L1](-)-[L3](-) and [1](-)-[3](-) occurs at the tpy-CO ligand as shown by UV/vis, IR, and EPR spectroscopy of the chemically generated radicals. Under rapid freezing conditions, radicals [2](-) and [3](-) are stabilized as different valence isomers with the odd electron localized at the [bpy-CO](•) bridging unit instead of the [tpy-CO](•). Furthermore, in radical [3](-) this valence equilibrium is shifted from [bpy-CO](•) to [tpy-CO](•) by coordination of [PF(6)](-) counterions to the bridging amide unit and back by replacing the [PF(6)](-) counterion with [BPh(4)](-). Photoinduced electron transfer (λ(exc) = 500 nm) to L1-L3 and to 1-3 is successful using triethanolamine (TEOA) as a reducing agent. Photocatalytic reduction of CO(2) by TEOA and 1-3 is hampered by the wrong site of electron localization in the one-electron reduced species [1](-)-[3](-).

Stable push‐pull substituted heteroleptic bis(tridentate) ruthenium(II) polypyridine complexes with COOH or 2,2′‐bipyridine anchor groups have been prepared and characterized by 1H, 13C and 15N NMR 1D and 2D spectroscopy, infrared spectroscopy, elemental analysis, high‐resolution ESI mass spectrometry, electrochemistry, UV/Vis absorption spectroscopy, luminescence spectroscopy, and density functional calculations. The complexes feature a pronounced electronic directionality and high absorption wavelengths up to λmax = 544 nm extending to 720 nm as a result of favorable push‐pull substitutions. A remarkable photostability in the presence of water and coordinating ions (I–) was discovered for the tridentate complexes when compared with the standard ruthenium sensitizer N719 and tris(bidentate) [Ru(bpy)3](PF6)2, which are highly photolabile under the same conditions (photodissociation/photosubstitution). The complexes were studied as photosensitizers in dye‐sensitized solar cells. The incident photon‐to‐current conversion efficiency follows the absorption spectra into the NIR region. However, the high positive charge of the complexes (2+) favors the recombination of the injected electrons with I3– of the redox electrolyte, which is evidenced by high dark currents and short electron recombination lifetimes, leading to low cell performances compared with cells with the negatively charged N719 dye.

Metalloligands L1 and L2 consisting of directional bis(terpyridine)ruthenium(II) units and bipyridine moieties were constructed by amide formation. From these metalloligands two Ru-Pt heterobimetallic complexes 1 and 2 were derived by a building-block method by means of platination with [PtCl 2 (dmso) 2 ]. Both bimetallic complexes 1 and 2 feature metal-to-ligand charge transfer (MLCT) absorptions, and emission occurs at room temperature in fluid solution from 3 MLCT(Ru) states in all cases. Energy transfer from platinum [a]

Atomic oxygen densities and fluences in a microwave plasma are determined by means of optical emission spectroscopy for different oxygen to hexamethyldisiloxane (HMDSO) ratios during deposition of SiO x and SiO x C y H z like coatings on molecularly defined organic surfaces. The plasma coatings are deposited on octadecanethiol self-assembled monolayers that serve as a sensor layer. They are used for tracing the interfacial changes induced during plasma deposition as a function of the O 2 to HMDSO ratio and absolutely quantified atomic oxygen fluence. The interfacial chemical changes are monitored by means of polarization modulation IR reflection-absorption spectroscopy. The data reveal that significant oxidative degradation of the sensor layer is reached for exposure to an atomic oxygen fluence of 1.0 Á 10 22 m À2 .

Front Cover: Spectroscopic investigations of plasma properties and polymer surface‐near regions reveal the oxidative degradation of polymer interface as a function of atomic oxygen fluence during deposition of silicon oxide films. The absolutely quantified atomic oxygen fluence is determined by means of optical emission spectroscopy. Self‐assembled monolayers are used to mimic an aliphatic polymer and to track the interfacial changes by PM‐IRRAS. The interface stays intact if the atomic oxygen fluence is kept below a certain value during deposition. Further details can be found in the article by Felix Mitschker et al. http://doi.wiley.com/10.1002/ppap.201500085.