We report the binding geometries of the isomers that are formed when the hydrogen oxalate ((CO2)2H=HOx) anion attaches to dinuclear coinage metal phosphine complexes of the form [M1M2dcpm2(HOx)]+ with M=Cu, Ag and dcpm=bis(dicyclohexylphosphino)methane, abbreviated [MM]+. These structures are established by comparison of isomer‐selective experimental vibrational band patterns displayed by the cryogenically cooled and N2‐tagged cations with DFT calculations of the predicted spectra for various local minima. Two isomeric classes are identified that feature either attachment of the carboxylate oxygen atoms to the two metal centers (end‐on docking) or attachment of oxygen atoms on different carbon atoms asymmetrically to the metal ions (side‐on docking). Within each class, there are additional isomeric variations according to the orientation of the OH group. This behavior indicates that HOx undergoes strong and directional coordination to [CuCu]+ but adopts a more flexible coordination to [AgAg]+. Infrared spectra of the bare ions, fragmentation thresholds and ion mobility measurements are reported to explore the behaviors of the complexes at ambient temperature.
What prompted you to investigate this system?In our collaborative research center "3MET"w ea re fascinated by metal-metal interactions, which determine the photo-physical/ chemical properties of molecular transition metal complexes and are hitherto not fully understood. Inspired by previous studies on multinuclear silver hydrides and our work on bimetallic phosphinestabilized compounds, we extended the nuclearity by designing a trimetallic system that allows for direct optical excitation of a metal-centered chromophore.
What was the inspiration for this cover design?In order to emphasize the UV-induced electron transfer within the [Ag 3 H] scaffold, we chose acomic style illustration which highlights the resulting enforcement of argentophilic interaction within the metal core. Having in mind the explorative spirit of the scientific field of metal complexes and its search for new frontiers, we imagined the vast expanses of the universe. Finally,i na nh omage to the 1980s film "Tron", we attempted to illustrate the abstract inner workings of aC PU running complex quantum chemical algorithms.
Does the research open other avenues that you would like to investigate?One aspect of the study which surprised us is the seemingly high reactivity of odd-electron silver hydride molecular ions towards dioxygen. Consequently,w ea re very curious about their molecular/ electronic structure, envisioning their gas phase spectroscopic and theoretical characterization. We plan to probe how different ligands and other metal centers control optical properties and photoreactivity of metal hydrides also gearing towards their luminescence and ultrafast electronic dynamics in both gas phase and solution.Invited for the cover of this issue aret he research groups of Rolf Diller,G ereon Niedner-Schatteburg, Christoph Riehn and Werner R. Thiel from the TU Kaiserslautern (TUK) and the group of Wim Klopper of the KarlsruheI nstitute of Technology (KIT) collaborating within the research center "3MET" (SFB/TRR 88). The image depicts the photoinitiated charge transfer within aphosphine-stabilized triangular silver hydride complex. Read the full text of the article at
UV‐induced hydride‐to‐silver elecTron transfer was evidenced by specific photofragments of mass‐selected dications of a bisphosphine‐stabilized triangular silver(I) hydride complex. The electronic transitions were authenticated by high‐level quantum chemical computations based on the GW method and Bethe–Salpeter equation (GW‐BSE). The unique [Ag3(μ3‐H)]2+ scaffold, featuring argentophilic interaction, was unequivocally verified by 1H NMR spectroscopy in concert with X‐ray structural analysis and DFT. More information can be found in the Full Paper by C. Riehn, W. R. Thiel, et al. on page 11269.
Invited for the cover of this issue are the research groups of Rolf Diller, Gereon Niedner‐Schatteburg, Christoph Riehn and Werner R. Thiel from the TU Kaiserslautern (TUK) and the group of Wim Klopper of the Karlsruhe Institute of Technology (KIT) collaborating within the research center “3MET” (SFB/TRR 88). The image depicts the photoinitiated charge transfer within a phosphine‐stabilized triangular silver hydride complex. Read the full text of the article at 10.1002/chem.201901981.
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