The reaction between indigo, H2Ind, and Ru(bpy)2(EtOH)22+ in EtOH/NaOH produced Ru(bpy)2(HInd)ClO4 1ClO4, rac-Ru(bpy)22(μ-Ind)(ClO4)2 2(ClO4)2, and meso-Ru(bpy)22(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)
%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 1ClO4, rac-Ru(bpy)22(μ-Ind)(ClO4)2 2(ClO4)2, and meso-Ru(bpy)22(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 = {2019-07-15T13:41:23.000+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/b_schwederski},
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 = {2019-07-15T11:42:10.000+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
}