%0 Journal Article %1 Chatterjee.2021 %A Chatterjee, Madhumita %A Mondal, Sudipta %A Hazari, Arijit Singha %A Zalis, Stanislav %A Kaim, Wolfgang %A Lahiri, Goutam Kumar %D 2021 %J Dalton Transactions %K imported %N 12 %P 4191-4201 %R 10.1039/d1dt00282a %T Variable electronic structure and spin distribution in bis(2,2'-bipyridine)-metal complexes (M = Ru or Os) of 4,5-dioxido- and 4,5-diimido-pyrene %V 50 %X The odd-electron compounds [M(bpy)2(L1)](ClO4) M = Ru ([1](ClO4)) or Os ([2](ClO4)), and the even-electron species [M(bpy)2(H2L2)](ClO4)2, M = Ru ([3](ClO4)2) or Os ([4](ClO4)2) were obtained from pyrene-4,5-dione, L1, or 4,5-diaminopyrene, H4L2, and were characterized structurally, electrochem. and spectroscopically. Exptl. and computational anal. (TD-DFT) revealed different electronic structures and spin distributions of the paramagnetic monocations 1+-4+. EPR studies and electronic absorption studies exhibit increasing metal contributions to the singly occupied MO along the series 1+ \textless 3+ \textless 4+ \textless 2+, illustrated by g value and long-wavelength absorbance. In addition to variations of the metal (Ru,Os) and the donor atoms (O,NH) the extension of the p system of the semiquinone-type ligand has a large effect on the electronic structure of the paramagnetic cations.

@article{Chatterjee.2021, abstract = {The odd-electron compounds [M(bpy)2(L1)](ClO4) M = Ru ([1](ClO4)) or Os ([2](ClO4)), and the even-electron species [M(bpy)2(H2L2)](ClO4)2, M = Ru ([3](ClO4)2) or Os ([4](ClO4)2) were obtained from pyrene-4,5-dione, L1, or 4,5-diaminopyrene, H4L2, and were characterized structurally, electrochem. and spectroscopically. Exptl. and computational anal. (TD-DFT) revealed different electronic structures and spin distributions of the paramagnetic monocations 1+-4+. EPR studies and electronic absorption studies exhibit increasing metal contributions to the singly occupied MO along the series 1+ {\textless} 3+ {\textless} 4+ {\textless} 2+, illustrated by g value and long-wavelength absorbance. In addition to variations of the metal (Ru,Os) and the donor atoms (O,NH) the extension of the \textgreek{p} system of the semiquinone-type ligand has a large effect on the electronic structure of the paramagnetic cations.}, added-at = {2022-06-15T12:05:25.000+0200}, author = {Chatterjee, Madhumita and Mondal, Sudipta and Hazari, Arijit Singha and Zalis, Stanislav and Kaim, Wolfgang and Lahiri, Goutam Kumar}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2d87da75de53a1d869562765b49e18960/huebleriac}, doi = {10.1039/d1dt00282a}, interhash = {01334a50349d9849100e7f4ddfe4dd15}, intrahash = {d87da75de53a1d869562765b49e18960}, issn = {1477-9226}, journal = {Dalton Transactions}, keywords = {imported}, number = 12, pages = {4191-4201}, timestamp = {2022-06-15T10:05:25.000+0200}, title = {Variable electronic structure and spin distribution in bis(2,2'-bipyridine)-metal complexes (M = Ru or Os) of 4,5-dioxido- and 4,5-diimido-pyrene}, volume = 50, year = 2021 }