%0 Journal Article %1 Ansari.2016 %A Ansari, Mohd. Asif %A Mandal, Abhishek %A Paretzki, Alexa %A Beyer, Katharina %A Fiedler, Jan %A Kaim, Wolfgang %A Lahiri, Goutam Kumar. %D 2016 %J Inorganic Chemistry %K bipyridine complex complex;electrochem complex;ruthenium crystal diaminoanthracenedione dinuclear mononuclear phenyldiazenylpyridine prepn ruthenium spectroelectrochem structure %N 11 %P 5655--5670 %R 10.1021/acs.inorgchem.6b00726 %T 1,5-Diamido-9,10-anthraquinone, a Centrosymmetric Redox-Active Bridge with Two Coupled b-Ketiminato Chelate Functions: Symmetric and Asymmetric Diruthenium Complexes %V 55 %X The dinuclear complexes (μ-H2L)[Ru(bpy)2]2(ClO4)2 ([3](ClO4)2), (μ-H2L)[Ru(pap)2]2(ClO4)2 ([4](ClO4)2), and the asym. [(bpy)2Ru(m-H2L)Ru(pap)2](ClO4)2 ([5](ClO4)2) were synthesized via the mononuclear species [Ru(H3L)(bpy)2]ClO4 ([1]ClO4) and [Ru(H3L)(pap)2]ClO4 ([2]ClO4), where H4L is the centrosym. 1,5-diamino-9,10-anthraquinone, bpy is 2,2'-bipyridine, and pap is 2-phenylazopyridine. Electrochem. of the structurally characterized [1]ClO4, [2]ClO4, [3](ClO4)2, [4](ClO4)2, and [5](ClO4)2 reveals multistep oxidn. and redn. processes, which were analyzed by EPR of paramagnetic intermediates and by UV-visible-NIR spectro-electrochem. With support by time-dependent d. functional theory (DFT) calcns. the redox processes could be assigned. Significant results include the dimetal/bridging ligand mixed spin distribution in 33+ vs. largely bridge-centered spin in 43+-a result of the presence of RuII-stabilizing pap coligands. In addn. to the metal/ligand alternative for electron transfer and spin location, the dinuclear systems allow for the observation of ligand/ligand and metal/metal site differentiation within the multistep redox series. DFT-supported EPR and NIR absorption spectroscopy of the latter case revealed class II mixed-valence behavior of the oxidized asym. system 53+ with about equal contributions from a radical bridge formulation. In comparison to the analogs with the deprotonated 1,4-diaminoanthraquinone isomer the centrosym. H2L2- bridge shows anodically shifted redox potentials and weaker electronic coupling between the chelate sites. [on SciFinder(R)]

@article{Ansari.2016, abstract = {The dinuclear complexes {(μ-H2L)[Ru(bpy)2]2}(ClO4)2 ([3](ClO4)2), {(μ-H2L)[Ru(pap)2]2}(ClO4)2 ([4](ClO4)2), and the asym. [(bpy)2Ru(\textgreek{m}-H2L)Ru(pap)2](ClO4)2 ([5](ClO4)2) were synthesized via the mononuclear species [Ru(H3L)(bpy)2]ClO4 ([1]ClO4) and [Ru(H3L)(pap)2]ClO4 ([2]ClO4), where H4L is the centrosym. 1,5-diamino-9,10-anthraquinone, bpy is 2,2'-bipyridine, and pap is 2-phenylazopyridine. Electrochem. of the structurally characterized [1]ClO4, [2]ClO4, [3](ClO4)2, [4](ClO4)2, and [5](ClO4)2 reveals multistep oxidn. and redn. processes, which were analyzed by EPR of paramagnetic intermediates and by UV-visible-NIR spectro-electrochem. With support by time-dependent d. functional theory (DFT) calcns. the redox processes could be assigned. Significant results include the dimetal/bridging ligand mixed spin distribution in 33+ vs. largely bridge-centered spin in 43+-a result of the presence of RuII-stabilizing pap coligands. In addn. to the metal/ligand alternative for electron transfer and spin location, the dinuclear systems allow for the observation of ligand/ligand and metal/metal site differentiation within the multistep redox series. DFT-supported EPR and NIR absorption spectroscopy of the latter case revealed class II mixed-valence behavior of the oxidized asym. system 53+ with about equal contributions from a radical bridge formulation. In comparison to the analogs with the deprotonated 1,4-diaminoanthraquinone isomer the centrosym. H2L2- bridge shows anodically shifted redox potentials and weaker electronic coupling between the chelate sites. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Ansari, Mohd. Asif and Mandal, Abhishek and Paretzki, Alexa and Beyer, Katharina and Fiedler, Jan and Kaim, Wolfgang and Lahiri, Goutam Kumar.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/26709b2814a058475e9ee49fb48f506b0/huebleriac}, doi = {10.1021/acs.inorgchem.6b00726}, interhash = {1a928eae2d766158e4047e82b4ea1ee9}, intrahash = {6709b2814a058475e9ee49fb48f506b0}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {bipyridine complex complex;electrochem complex;ruthenium crystal diaminoanthracenedione dinuclear mononuclear phenyldiazenylpyridine prepn ruthenium spectroelectrochem structure}, number = 11, pages = {5655--5670}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {1,5-Diamido-9,10-anthraquinone, a Centrosymmetric Redox-Active Bridge with Two Coupled \textgreek{b}-Ketiminato Chelate Functions: Symmetric and Asymmetric Diruthenium Complexes}, volume = 55, year = 2016 }