Analysis of Redox Series of Unsymmetrical 1,4-Diamido-9,10-anthraquinone-Bridged
Diruthenium Compounds
Abhishek Mandal
Md Asmaul Hoque
Anita Grupp
Alexa Paretzki
Wolfgang Kaim
Goutam Kumar Lahiri
10.1021/acs.inorgchem.5b02541.s004
https://acs.figshare.com/articles/dataset/Analysis_of_Redox_Series_of_Unsymmetrical_1_4_Diamido_9_10_anthraquinone_Bridged_Diruthenium_Compounds/2305348
The unsymmetrical diruthenium complexes
[(bpy)<sub>2</sub>Ru<sup>II</sup>(μ-H<sub>2</sub>L<sup>2–</sup>)Ru<sup>III</sup>(acac)<sub>2</sub>]ClO<sub>4</sub> ([<b>3</b>]ClO<sub>4</sub>), [(pap)<sub>2</sub>Ru<sup>II</sup>(μ-H<sub>2</sub>L<sup>2–</sup>)Ru<sup>III</sup>(acac)<sub>2</sub>]ClO<sub>4</sub> ([<b>4</b>]ClO<sub>4</sub>), and [(bpy)<sub>2</sub>Ru<sup>II</sup>(μ-H<sub>2</sub>L<sup>2–</sup>)Ru<sup>II</sup>(pap)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub> ([<b>5</b>](ClO<sub>4</sub>)<sub>2</sub>) have been obtained by way of the
mononuclear precursors [(bpy)<sub>2</sub>Ru<sup>II</sup>(H<sub>3</sub>L<sup>–</sup>)]ClO<sub>4</sub> ([<b>1</b>]ClO<sub>4</sub>) and [(pap)<sub>2</sub>Ru<sup>II</sup>(H<sub>3</sub>L<sup>–</sup>)]ClO<sub>4</sub> ([<b>2</b>]ClO<sub>4</sub>) (where bpy =
2,2′-bipyridine, pap = 2-phenylazopyridine, acac<sup>–</sup> = 2,4-pentanedionate, and H<sub>4</sub>L = 1,4-diamino-9,10-anthraquinone).
Structural characterization by single-crystal X-ray diffraction and
magnetic resonance (nuclear magnetic resonance (NMR), electron paramagnetic
resonance (EPR)) were used to establish the oxidation state situation
in each of the isolated materials. Cyclic voltammetry, EPR, and ultraviolet–visible–near-infrared
(UV-vis-NIR) spectroelectrochemistry were used to analyze the multielectron
transfer series of the potentially class I mixed-valent dinuclear
compounds, considering the redox activities of differently coordinated
metals, of the noninnocent bridge and of the terminal ligands. Comparison
with symmetrical analogues [L<sub>2</sub><sup>′</sup>Ru(μ-H<sub>2</sub>L)RuL<sub>2</sub><sup>′</sup>]<sup><i>n</i></sup> (where L′ = bpy, pap, or acac<sup>–</sup>) shows that the redox processes in the unsymmetrical dinuclear compounds
are not averaged, with respect to the corresponding symmetrical systems,
because of intramolecular charge rearrangements involving the metals,
the noninnocent bridge, and the ancillary ligands.
2016-02-18 00:00:00
EPR
ligand
unsymmetrical dinuclear compounds
bpy
acac
resonance
ClO
multielectron transfer series
redox
NMR
intramolecular charge rearrangements
oxidation state situation
pap
4L
noninnocent bridge