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Ancillary Ligand Control of Electronic Structure in o-Benzoquinonediimine-Ruthenium Complex Redox Series: Structures, Electron Paramagnetic Resonance (EPR), and Ultraviolet-Visible-Near-Infrared (UV-vis-NIR) Spectroelectrochemistry

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Title Ancillary Ligand Control of Electronic Structure in o-Benzoquinonediimine-Ruthenium Complex Redox Series: Structures, Electron Paramagnetic Resonance (EPR), and Ultraviolet-Visible-Near-Infrared (UV-vis-NIR) Spectroelectrochemistry
 
Creator DAS, A
GHOSH, P
PLEBST, S
SCHWEDERSKI, B
MOBIN, SM
KAIM, W
LAHIRI, GK
 
Subject DENSITY-FUNCTIONAL THEORY
OXIDATIVE DIMERIZATION
EXCITATION-ENERGIES
AB-INITIO
ELECTROCHEMISTRY
MOLECULES
DIIMINES
2-PHENYLAZOPYRIDINE
IMINOTHIOQUINONE
ACETYLACETONATE
 
Description The compounds Ru(acac)(2)(Q) (1), [Ru(bpy)(2)(Q)](ClO4)(2) ([2](ClO4)(2)), and [Ru(pap)(2)(Q)]PF6 ([3]PF6), containing Q = N,N'-diphenyl-o-benzoquinonediimine and donating 2,4-pentanedionate ligands (acac), pi-accepting 2,2/-bipyridine (bpy), or strongly pi-accepting 2-phenylazopyridine (pap) were prepared and structurally identified. The electronic structures of the complexes and several accessible oxidized and reduced forms were studied experimentally (electrochemistry, magnetic resonance, ultraviolet-visible-near-infrared (UV-vis-NIR) spectroelectrochemistry) and computationally (DFT/TD-DFT) to reveal significantly variable electron transfer behavior and charge distribution. While the redox system 1+1 prefers trivalent ruthenium with corresponding oxidation states Q(0)-Q(2-) of the noninnocent ligand, the series 2(2+)-2(0) and 3(2+)-3(-) retain Ru-II. The bpy and pap co-ligands are not only spectators but can also be reduced prior to a second reduction of Q. The present study with new experimental and computational evidence on the influence of co-ligands on the metal is complementary to a report on the substituent effects in o-quinonediimine ligands [Kalinina et al., Inorg. Chem. 2008, 47, 10110] and to the discussion of the most appropriate oxidation state formulation Ru-II(Q(0)) or Ru-III(Q(.-)).
 
Publisher AMER CHEMICAL SOC
 
Date 2016-01-15T06:25:36Z
2016-01-15T06:25:36Z
2015
 
Type Article
 
Identifier INORGANIC CHEMISTRY, 54(7)3376-3386
0020-1669
1520-510X
http://dx.doi.org/10.1021/ic503070j
http://dspace.library.iitb.ac.in/jspui/handle/100/17927
 
Language en