Epindolidione (H2L), a heteroatom-modified analog of tetracene and a structural isomer of indigo, forms dinuclear complexes with [RuX2]2+, X = bpy (2,2'-bipyridine, [1]2+) or pap (2-phenylazopyridine, [2]2+), in its doubly deprotonated bridging form m-L2-. The dications in compounds meso-[1](ClO4)2 and meso-[2](ClO4)2, [X2Ru(m-L)RuX2](ClO4)2, contain five-membered chelate rings N-C-C-O-RuII with p bridged metals at an intramol. distance of 7.19 \AA. Stepwise reversible oxidation and reduction is mainly ligand centered (oxidation: L2-; reduction: X), as deduced from EPR of one-electron oxidized and reduced intermediates and from UV/Vis/NIR spectroelectrochem., supported by TD-DFT calculation results. The results for [1](ClO4)2 and [2](ClO4)2 are qual. similar to the ones observed with the deprotonated indigo-bridged isomers with their six-membered chelate ring structures, confirming the suitability of both p systems for mol. electronics applications, low-energy absorptions, and multiple electron transfers.
%0 Journal Article
%1 Kumari.2021
%A Kumari, Maya
%A Bera, Sudip Kumar
%A Blickle, Svenja
%A Kaim, Wolfgang
%A Lahiri, Goutam Kumar
%D 2021
%J Chemistry - A European Journal
%K imported
%N 17
%P 5461-5469
%R 10.1002/chem.202004747
%T The Indigo Isomer Epindolidione as a Redox-Active Bridging Ligand for Diruthenium Complexes
%V 27
%X Epindolidione (H2L), a heteroatom-modified analog of tetracene and a structural isomer of indigo, forms dinuclear complexes with [RuX2]2+, X = bpy (2,2'-bipyridine, [1]2+) or pap (2-phenylazopyridine, [2]2+), in its doubly deprotonated bridging form m-L2-. The dications in compounds meso-[1](ClO4)2 and meso-[2](ClO4)2, [X2Ru(m-L)RuX2](ClO4)2, contain five-membered chelate rings N-C-C-O-RuII with p bridged metals at an intramol. distance of 7.19 \AA. Stepwise reversible oxidation and reduction is mainly ligand centered (oxidation: L2-; reduction: X), as deduced from EPR of one-electron oxidized and reduced intermediates and from UV/Vis/NIR spectroelectrochem., supported by TD-DFT calculation results. The results for [1](ClO4)2 and [2](ClO4)2 are qual. similar to the ones observed with the deprotonated indigo-bridged isomers with their six-membered chelate ring structures, confirming the suitability of both p systems for mol. electronics applications, low-energy absorptions, and multiple electron transfers.
@article{Kumari.2021,
abstract = {Epindolidione (H2L), a heteroatom-modified analog of tetracene and a structural isomer of indigo, forms dinuclear complexes with [RuX2]2+, X = bpy (2,2'-bipyridine, [1]2+) or pap (2-phenylazopyridine, [2]2+), in its doubly deprotonated bridging form \textgreek{m}-L2-. The dications in compounds meso-[1](ClO4)2 and meso-[2](ClO4)2, [X2Ru(\textgreek{m}-L)RuX2](ClO4)2, contain five-membered chelate rings N-C-C-O-RuII with \textgreek{p} bridged metals at an intramol. distance of 7.19 {\AA}. Stepwise reversible oxidation and reduction is mainly ligand centered (oxidation: L2-; reduction: X), as deduced from EPR of one-electron oxidized and reduced intermediates and from UV/Vis/NIR spectroelectrochem., supported by TD-DFT calculation results. The results for [1](ClO4)2 and [2](ClO4)2 are qual. similar to the ones observed with the deprotonated indigo-bridged isomers with their six-membered chelate ring structures, confirming the suitability of both \textgreek{p} systems for mol. electronics applications, low-energy absorptions, and multiple electron transfers.},
added-at = {2022-06-15T12:05:25.000+0200},
author = {Kumari, Maya and Bera, Sudip Kumar and Blickle, Svenja and Kaim, Wolfgang and Lahiri, Goutam Kumar},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/25233d46ea36ac4f35d3350338c5abc66/huebleriac},
doi = {10.1002/chem.202004747},
interhash = {6093fc85260cfdbab613680ff4eacd13},
intrahash = {5233d46ea36ac4f35d3350338c5abc66},
issn = {0947-6539},
journal = {Chemistry - A European Journal},
keywords = {imported},
number = 17,
pages = {5461-5469},
timestamp = {2022-06-15T10:05:25.000+0200},
title = {The Indigo Isomer Epindolidione as a Redox-Active Bridging Ligand for Diruthenium Complexes},
volume = 27,
year = 2021
}
