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Electron-Rich Diruthenium Complexes with π-Extended Alkenyl Ligands and Their F<sub>4</sub>TCNQ Charge-Transfer Salts

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

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DAS, Rajorshi, Michael LINSEIS, Stefan M. 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

@article{Das2022-04-22Elect-56823, title={Electron-Rich Diruthenium Complexes with π-Extended Alkenyl Ligands and Their F4TCNQ Charge-Transfer Salts}, year={2022}, doi={10.1002/chem.202104403}, number={23}, volume={28}, issn={0947-6539}, journal={Chemistry - A European Journal}, author={Das, Rajorshi and Linseis, Michael and Schupp, Stefan M. and Schmidt-Mende, Lukas and Winter, Rainer F.}, note={Article Number: e202104403} }

Schupp, Stefan M. eng terms-of-use Linseis, Michael Winter, Rainer F. Linseis, Michael Winter, Rainer F. Schmidt-Mende, Lukas 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. Electron-Rich Diruthenium Complexes with π-Extended Alkenyl Ligands and Their F<sub>4</sub>TCNQ Charge-Transfer Salts 2022-03-11T08:36:16Z 2022-03-11T08:36:16Z Schupp, Stefan M. 2022-04-22 Schmidt-Mende, Lukas Das, Rajorshi Das, Rajorshi

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