%0 Journal Article %1 Roy.2009 %A Roy, Sayak %A Sarkar, Biprajit %A Duboc, Carole %A Fiedler, Jan %A Sarper, Orkan %A Lissner, Falk %A Mobin, Shaikh M. %A Lahiri, Goutam Kumar %A Kaim, Wolfgang %D 2009 %J Chemistry (Weinheim an der Bergstrasse, Germany) %K imported %N 28 %P 6932--6939 %T Heterohexanuclear (Cu3Fe3) complexes of substituted hexaazatrinaphthylene (HATN) ligands: Twofold BF4(-) association in the solid and stepwise oxidation (3e) or reduction (2e) to spectroelectrochemically characterized species %V 15 %X New tris(ferrocenylcopper) compounds (mu(3)-dqp)Cu(dppf)(3)X(3) (dppf = 1,1'-bis(diphenylphosphinoferrocene), dqp = hexamethyl-, hexachloro- or un-substituted diquinoxalino2,3-a:2',3'-cphenazine = hexaazatrinaphthylene (HATN), X(-) = BF(4)(-) or PF(6)(-)) undergo at least two different, reversible one-electron reductions and three very closely spaced one-electron oxidations. While the latter are attributed to the stepwise ferrocene--\textgreaterferrocenium conversions, the first electron addition occurs in the ligand bridge to yield EPR detectable radical complexes. X-band EPR measurements at 9.5 GHz showed a partially resolved hyperfine structure, while high-frequency EPR measurements at 95 or 115 GHz revealed a small but variable axial g tensor anisotropy. All reversible steps were investigated by optically transparent thin-layer electrode (OTTLE) spectroelectrochemistry (UV/Vis/NIR regions), revealing very low energy transitions for the reduced forms in agreement with the frontier MO arrangement. A crystal structure of the compound with unsubstituted dqp shows notable deviation from the trigonal symmetry and the close association of two tetrafluoroborate anions with the complex trication along the quasi-trigonal axis to yield (mu(3)-dqp)Cu(dppf)(3)(BF(4))(2)BF(4).on SciFinder (R)

@article{Roy.2009, abstract = {New tris(ferrocenylcopper) compounds [(mu(3)-dqp){Cu(dppf)}(3)][X](3) (dppf = 1,1'-bis(diphenylphosphinoferrocene), dqp = hexamethyl-, hexachloro- or un-substituted diquinoxalino[2,3-a:2',3'-c]phenazine = hexaazatrinaphthylene (HATN), X(-) = BF(4)(-) or PF(6)(-)) undergo at least two different, reversible one-electron reductions and three very closely spaced one-electron oxidations. While the latter are attributed to the stepwise ferrocene--{\textgreater}ferrocenium conversions, the first electron addition occurs in the ligand bridge to yield EPR detectable radical complexes. X-band EPR measurements at 9.5 GHz showed a partially resolved hyperfine structure, while high-frequency EPR measurements at 95 or 115 GHz revealed a small but variable axial g tensor anisotropy. All reversible steps were investigated by optically transparent thin-layer electrode (OTTLE) spectroelectrochemistry (UV/Vis/NIR regions), revealing very low energy transitions for the reduced forms in agreement with the frontier MO arrangement. A crystal structure of the compound with unsubstituted dqp shows notable deviation from the trigonal symmetry and the close association of two tetrafluoroborate anions with the complex trication along the quasi-trigonal axis to yield [(mu(3)-dqp){Cu(dppf)}(3)(BF(4))(2)]BF(4).[on SciFinder (R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Roy, Sayak and Sarkar, Biprajit and Duboc, Carole and Fiedler, Jan and Sarper, Orkan and Lissner, Falk and Mobin, Shaikh M. and Lahiri, Goutam Kumar and Kaim, Wolfgang}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2b85b795c751720b584d1ded0ccfe6e56/huebleriac}, interhash = {f1209036cfb4de9e0421f935496d5564}, intrahash = {b85b795c751720b584d1ded0ccfe6e56}, issn = {1521-3765}, journal = {Chemistry (Weinheim an der Bergstrasse, Germany)}, keywords = {imported}, number = 28, pages = {6932--6939}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Heterohexanuclear (Cu3Fe3) complexes of substituted hexaazatrinaphthylene (HATN) ligands: Twofold BF4(-) association in the solid and stepwise oxidation (3e) or reduction (2e) to spectroelectrochemically characterized species}, volume = 15, year = 2009 }