Electronic Structure of the Water Oxidation Catalyst cis,cis-[(bpy)2(H2O)RuIIIORuIII(OH2)(bpy)2]4+, The Blue Dimer
Citations Over TimeTop 10% of 2012 papers
Abstract
The first designed molecular catalyst for water oxidation is the "blue dimer", cis,cis-[(bpy)(2)(H(2)O)Ru(III)ORu(III)(OH(2))(bpy)(2)](4+). Although there is experimental evidence for extensive electronic coupling across the μ-oxo bridge, results of earlier DFT and CASSCF calculations provide a model with magnetic interactions of weak to moderately coupled Ru(III) ions across the μ-oxo bridge. We present the results of a comprehensive experimental investigation, combined with DFT calculations. The experiments demonstrate both that there is strong electronic coupling in the blue dimer and that its effects are profound. Experimental evidence has been obtained from molecular structures and key bond distances by XRD, electrochemically measured comproportionation constants for mixed-valence equilibria, temperature-dependent magnetism, chemical properties (solvent exchange, redox potentials, and pK(a) values), XPS binding energies, analysis of excitation-dependent resonance Raman profiles, and DFT analysis of electronic absorption spectra. The spectrum can be assigned based on a singlet ground state with specific hydrogen-bonding interactions with solvent molecules included. The results are in good agreement with available experimental data. The DFT analysis provides assignments for characteristic absorption bands in the near-IR and visible regions. Bridge-based dπ → dπ* and interconfiguration transitions at Ru(III) appear in the near-IR and MLCT and LMCT transitions in the visible. Reasonable values are also provided by DFT analysis for experimentally observed bond distances and redox potentials. The observed temperature-dependent magnetism of the blue dimer is consistent with a delocalized, diamagnetic singlet state (dπ(1)*)(2) with a low-lying, paramagnetic triplet state (dπ(1)*)(1)(dπ(2)*)(1). Systematic structural-magnetic-IR correlations are observed between ν(sym)(RuORu) and ν(asym)(RuORu) vibrational energies and magnetic properties in a series of ruthenium-based, μ-oxo-bridged complexes. Consistent with the DFT electronic structure model, bending along the Ru-O-Ru axis arises from a Jahn-Teller distortion with ∠Ru-O-Ru dictated by the distortion and electron-electron repulsion.
Related Papers
- → Reversible-Deactivation Radical Polymerization in the Presence of Metallic Copper. Comproportionation–Disproportionation Equilibria and Kinetics(2013)97 cited
- → Comproportionation and disproportionation in nickel and copper complexes(2023)78 cited
- → Effect of Comproportionation on Voltammograms for Two-Electron Reactions with an Irreversible Second Electron Transfer(1999)42 cited
- → Forming delocalized intermediate states with realistic quantum dots(2012)9 cited
- → Disproportionation, internal redox and comproportionation in the reaction of Hg22+ with WS42−: synthesis and structure of a novel mixed crystal, (PPh4)2[{Hg2(S)2}0.333(W2S6)0.666](1999)