Electron-Rich Diruthenium Complexes with π-Extended Alkenyl Ligands and Their F4TCNQ Charge-Transfer Salts

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Chemistry - A European Journal ; 28 (2022), 23. - e202104403. - Wiley. - ISSN 0947-6539. - eISSN 1521-3765
Abstract
The synthesis of dinuclear ruthenium alkenyl complexes with {Ru(CO)(Pi Pr3 )2 (L)} entities (L=Cl- in complexes Ru2 -3 and Ru2 -7; L=acetylacetonate (acac- ) in complexes Ru2 -4 and Ru2 -8) and with π-conjugated 2,7-divinylphenanthrenediyl (Ru2 -3, Ru2 -4) or 5,8-divinylquinoxalinediyl (Ru2 -7, Ru2 -8) as bridging ligands are reported. The bridging ligands are laterally π-extended by anellating a pyrene (Ru2 -7, Ru2 -8) or a 6,7-benzoquinoxaline (Ru2 -3, Ru2 -4) π-perimeter. This was done with the hope that the open π-faces of the electron-rich complexes will foster association with planar electron acceptors via π-stacking. The dinuclear complexes were subjected to cyclic and square-wave voltammetry and were characterized in all accessible redox states by IR, UV/Vis/NIR and, where applicable, by EPR spectroscopy. These studies signified the one-electron oxidized forms of divinylphenylene-bridged complexes Ru2 -7, Ru2 -8 as intrinsically delocalized mixed-valent species, and those of complexes Ru2 -3 and Ru2 -4 with the longer divinylphenanthrenediyl linker as partially localized on the IR, yet delocalized on the EPR timescale. The more electron-rich acac- congeners formed non-conductive 1 : 1 charge-transfer (CT) salts on treatment with the F4 TCNQ electron acceptor. All spectroscopic techniques confirmed the presence of pairs of complex radical cations and F4 TCNQ.- radical anions in these CT salts, but produced no firm evidence for the relevance of π-stacking to their formation and properties.
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ISO 690DAS, Rajorshi, Michael LINSEIS, Stefan SCHUPP, Lukas SCHMIDT-MENDE, Rainer F. WINTER, 2022. Electron-Rich Diruthenium Complexes with π-Extended Alkenyl Ligands and Their F4TCNQ Charge-Transfer Salts. In: Chemistry - A European Journal. Wiley. 28(23), e202104403. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.202104403
BibTex
@article{Das2022-04-22Elect-56823,
  year={2022},
  doi={10.1002/chem.202104403},
  title={Electron-Rich Diruthenium Complexes with π-Extended Alkenyl Ligands and Their F<sub>4</sub>TCNQ Charge-Transfer Salts},
  number={23},
  volume={28},
  issn={0947-6539},
  journal={Chemistry - A European Journal},
  author={Das, Rajorshi and Linseis, Michael and Schupp, Stefan and Schmidt-Mende, Lukas and Winter, Rainer F.},
  note={Article Number: e202104403}
}
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