Mixed-Valent Ruthenocene-Vinylruthenium Conjugates: Valence Delocalization Despite Chemically Different Redox Sites.
Christopher HassenrückAndré MangRainer F WinterPublished in: Inorganic chemistry (2019)
Ruthenocene-vinylruthenium conjugates Rc/Rc*-CH═CH-Ru(CO)(L)(P iPr3)2 (Rc = (η5-C5H5)Ru(η5-C5H4); Rc* = (η5-C5Me5)Ru(η5-C5H4); L = Cl or κ O, O' -acetylacetonato) have been prepared and investigated in their neutral, mono-, and dioxidized states by cyclic voltammetry, IR and UV/vis/NIR spectroelectrochemistry, and EPR spectroscopy. Their corresponding radical cations are (almost) completely delocalized mixed-valent systems as indicated by the low half-widths, the absence of solvatochromism, and the low-energy cutoff of their IVCT bands in the near-infrared (NIR) and their IR and EPR spectroscopic signatures. The degree of electronic coupling even exceeds that of their ferrocene analogs despite comparable differences between the intrinsic half-wave potentials of the vinylruthenium and the metallocenyl entities and substantially smaller half-wave potential splittings, Δ E1/2, in the ruthenocene congeners. All experimental results are backed by quantum chemical calculations.
Keyphrases
- energy transfer
- room temperature
- molecular docking
- molecular dynamics
- photodynamic therapy
- cancer therapy
- fluorescence imaging
- drug release
- fluorescent probe
- ionic liquid
- high resolution
- molecular dynamics simulations
- density functional theory
- single molecule
- quantum dots
- dna methylation
- gene expression
- atomic force microscopy
- human health
- mass spectrometry
- solid state
- electron transfer