%0 Journal Article %1 Chatterjee.2017 %A Chatterjee, Madhumita %A Mondal, Prasenjit %A Beyer, Katharina %A Paretzki, Alexa %A Kaim, Wolfgang %A Lahiri, Goutam Kumar. %D 2017 %J Dalton Transactions %K DFT bipyridine complex crystal density dinuclear dinuclear;electrochem dinuclear;electron dinuclear;ruthenium electronic indigo mononuclear prepn redox ruthenium spin structure;spectroelectrochem transition %N 15 %P 5091--5102 %R 10.1039/C7DT00055C %T A structurally characterised redox pair involving an indigo radical: Indigo based redox activity in complexes with one or two [Ru(bpy)2] fragments %V 46 %X The reaction between indigo, H2Ind, and Ru(bpy)2(EtOH)22+ in EtOH/NaOH produced [Ru(bpy)2(HInd)]ClO4 [1]ClO4, rac-[Ru(bpy)2]2(μ-Ind)(ClO4)2 [2](ClO4)2, and meso-[Ru(bpy)2]2(μ-Ind)(ClO4)3 [2](ClO4)3, which were structurally characterized, the latter as the first stable, isolable radical complex of indigo. The redox pair 22+/23+ showed little structural difference, as confirmed using DFT calcns. The redox series 1n and 2n were studied using voltammetry and spectroelectrochem. (EPR, UV-visible-NIR). Remarkably, the EPR results for 1, 12+, 2+ and 23+ revealed mostly ligand-based spin in Ru(II) complexes of the indigo-derived radical ligands HInd.bul.2-, HInd.bul., Ind.bul.3- and Ind.bul.-, in agreement with the DFT calcd. spin densities. The dominance of the frontier orbitals by the metal-stabilized indigo chromophore was also confirmed via the TD-DFT based assignment of near-IR absorptions as intra-indigo or ligand-to-ligand charge transfer transitions. [on SciFinder(R)]

@article{Chatterjee.2017, abstract = {The reaction between indigo, H2Ind, and {Ru(bpy)2(EtOH)2}2+ in EtOH/NaOH produced [Ru(bpy)2(HInd)]ClO4 [1]ClO4, rac-{[Ru(bpy)2]2(μ-Ind)}(ClO4)2 [2](ClO4)2, and meso-{[Ru(bpy)2]2(μ-Ind)}(ClO4)3 [2](ClO4)3, which were structurally characterized, the latter as the first stable, isolable radical complex of indigo. The redox pair 22+/23+ showed little structural difference, as confirmed using DFT calcns. The redox series 1n and 2n were studied using voltammetry and spectroelectrochem. (EPR, UV-visible-NIR). Remarkably, the EPR results for 1, 12+, 2+ and 23+ revealed mostly ligand-based spin in Ru(II) complexes of the indigo-derived radical ligands HInd.bul.2-, HInd.bul., Ind.bul.3- and Ind.bul.-, in agreement with the DFT calcd. spin densities. The dominance of the frontier orbitals by the metal-stabilized indigo chromophore was also confirmed via the TD-DFT based assignment of near-IR absorptions as intra-indigo or ligand-to-ligand charge transfer transitions. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Chatterjee, Madhumita and Mondal, Prasenjit and Beyer, Katharina and Paretzki, Alexa and Kaim, Wolfgang and Lahiri, Goutam Kumar.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2c3de132b16a417d57d3dd16f5c2a9b32/huebleriac}, doi = {10.1039/C7DT00055C}, interhash = {aadad110d6b4a72d9dd6b0fbd0c9bc12}, intrahash = {c3de132b16a417d57d3dd16f5c2a9b32}, issn = {1477-9226}, journal = {Dalton Transactions}, keywords = {DFT bipyridine complex crystal density dinuclear dinuclear;electrochem dinuclear;electron dinuclear;ruthenium electronic indigo mononuclear prepn redox ruthenium spin structure;spectroelectrochem transition}, number = 15, pages = {5091--5102}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {A structurally characterised redox pair involving an indigo radical: Indigo based redox activity in complexes with one or two [Ru(bpy)2] fragments}, volume = 46, year = 2017 }