%0 Journal Article %1 Frantz.2002 %A Frantz, Stephanie %A Hartmann, Heiko %A Doslik, Natasa %A Wanner, Matthias %A Kaim, Wolfgang %A Kuemmerer, Hans-Juergen %A Denninger, Gert %A Barra, Anne-Laure %A Duboc-Toia, Carole %A Fiedler, Jan %A Ciofini, Ilaria %A Urban, Christian %A Kaupp, Martin. %D 2002 %J Journal of the American Chemical Society %K EPR complex complex;UV complex;spin density g multifrequency organo persistent radical rhenium spectra tensor visible %N 35 %P 10563--10571 %R 10.1021/ja025829n %T Multifrequency EPR Study and Density Functional g-Tensor Calculations of Persistent Organorhenium Radical Complexes %V 124 %X The dinuclear radical anion complexes (μ-L)Re(CO)3Cl2.bul.-, L = 2,2'-azobispyridine (abpy) and 2,2'-azobis(5-chloropyrimidine) (abcp), were studied by EPR at 9.5, 94, 230, and 285 GHz (abpy complex) and at 9.5 and 285 GHz (abcp complex). Whereas the X-band measurements yielded only the isotropic metal hyperfine coupling of the 185,187Re isotopes, the high-frequency EPR expts. in glassy frozen CH2Cl2/toluene soln. revealed the g components. Both the a(185,187Re) value and the g anisotropy, g1 - g3, are larger for the abcp complex, which contains the better p-accepting bridging ligand. Confirmation for this comes also from IR and UV/visible spectroscopy of the new (μ-abcp)Re(CO)3Cl2o/.bul.-/2- redox system. The g values are reproduced reasonably well by d. functional calcns. which confirm higher metal participation at the singly occupied MO and therefore larger contributions from the metal atoms to the g anisotropy in abcp systems compared to abpy complexes. Addnl. calcns. for systems (μ-abcp)M(CO)3X2.bul.- (M = Tc or Re and X = Cl, and X = F, Cl, or Br with M = Re) provided further insight into the relation between spin d. distribution and g anisotropy. on SciFinder(R)

@article{Frantz.2002, abstract = {The dinuclear radical anion complexes {(μ-L)[Re(CO)3Cl]2}.bul.-, L = 2,2'-azobispyridine (abpy) and 2,2'-azobis(5-chloropyrimidine) (abcp), were studied by EPR at 9.5, 94, 230, and 285 GHz (abpy complex) and at 9.5 and 285 GHz (abcp complex). Whereas the X-band measurements yielded only the isotropic metal hyperfine coupling of the 185,187Re isotopes, the high-frequency EPR expts. in glassy frozen CH2Cl2/toluene soln. revealed the g components. Both the a(185,187Re) value and the g anisotropy, g1 - g3, are larger for the abcp complex, which contains the better \textgreek{p}-accepting bridging ligand. Confirmation for this comes also from IR and UV/visible spectroscopy of the new {(μ-abcp)[Re(CO)3Cl]2}o/.bul.-/2- redox system. The g values are reproduced reasonably well by d. functional calcns. which confirm higher metal participation at the singly occupied MO and therefore larger contributions from the metal atoms to the g anisotropy in abcp systems compared to abpy complexes. Addnl. calcns. for systems {(μ-abcp)[M(CO)3X]2}.bul.- (M = Tc or Re and X = Cl, and X = F, Cl, or Br with M = Re) provided further insight into the relation between spin d. distribution and g anisotropy. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Frantz, Stephanie and Hartmann, Heiko and Doslik, Natasa and Wanner, Matthias and Kaim, Wolfgang and Kuemmerer, Hans-Juergen and Denninger, Gert and Barra, Anne-Laure and Duboc-Toia, Carole and Fiedler, Jan and Ciofini, Ilaria and Urban, Christian and Kaupp, Martin.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/24d706dcb4a19a406cc9383fec48be027/huebleriac}, doi = {10.1021/ja025829n}, interhash = {171b2796c8cc6986ef821d23de1ae9a2}, intrahash = {4d706dcb4a19a406cc9383fec48be027}, issn = {0002-7863}, journal = {Journal of the American Chemical Society}, keywords = {EPR complex complex;UV complex;spin density g multifrequency organo persistent radical rhenium spectra tensor visible}, number = 35, pages = {10563--10571}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Multifrequency EPR Study and Density Functional g-Tensor Calculations of Persistent Organorhenium Radical Complexes}, volume = 124, year = 2002 }