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- W2230361973 abstract "This work describes syntheses and electrochemical, spectroscopic, and bonding properties in a new series of dinuclear ruthenium(II) complexes bridged by polyaromatic (biphenyl, fluorene, phenanthrene, and pyrene) alkynyl ligands. Longitudinal expansion of the π-conjugated polyaromatic core of the bridging ligands caused a reduced potential difference between the anodic steps and reinforced their bridge-localized nature, as evidenced by UV/vis/near-IR and IR spectroelectrochemical data combined with DFT and TDDFT calculations. Importantly, the intricate multiple IR ν(C≡C) absorption bands for the singly oxidized states imply a thermal population of a range of conformers (rotamers) with distinct electronic character. This behavior was demonstrated with more accurate DFT calculations of selected nontruncated 1e– oxidized complexes in three different conformations. The combined experimental and theoretical data reveal that thermally populated rotamers featuring various mutual orientations of the ligated metal termini and the bridging diethynyl polyaromatic moieties have a significant impact on the electronic absorption and ν(C≡C) wavenumbers of the singly oxidized systems." @default.
- W2230361973 created "2016-06-24" @default.
- W2230361973 creator A5000251455 @default.
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- W2230361973 creator A5090618642 @default.
- W2230361973 date "2015-08-12" @default.
- W2230361973 modified "2023-10-15" @default.
- W2230361973 title "Diruthenium Complexes with Bridging Diethynyl Polyaromatic Ligands: Synthesis, Spectroelectrochemistry, and Theoretical Calculations" @default.
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- W2230361973 doi "https://doi.org/10.1021/acs.organomet.5b00276" @default.