A structurally characterised redox pair involving an indigo radical: Indigo based redox activity in complexes with one or two Ru(bpy)2 fragments

, , , , , und . Dalton Transactions 46 (15): 5091--5102 (2017)


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)

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