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
The compds. Ru(acac)2(Q) (1), Ru(bpy)2(Q)(ClO4)2 (2(ClO4)2), and Ru(pap)2(Q)PF6 (3PF6), contg. Q = N,N'-diphenyl-o-benzoquinonediimine and donating 2,4-pentanedionate ligands (acac-), p-accepting 2,2'-bipyridine (bpy), or strongly p-accepting 2-phenylazopyridine (pap) were prepd. and structurally identified. The electronic structures of the complexes and several accessible oxidized and reduced forms were studied exptl. (electrochem., magnetic resonance, UV-visible-near-IR (UV-visible-NIR) spectroelectrochem.) 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 oxidn. states Q0-Q2- of the noninnocent ligand, the series 22+-20 and 32+-3- retain RuII. The bpy and pap co-ligands are not only spectators but can also be reduced prior to a second redn. of Q. The present study with new exptl. 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 oxidn. state formulation RuII(Q0) or RuIII(Q.bul.-). on SciFinder(R)
%0 Journal Article
%1 Das.2015
%A Das, Ankita
%A Ghosh, Prabir
%A Plebst, Sebastian
%A Schwederski, Brigitte
%A Mobin, Shaikh M.
%A Kaim, Wolfgang
%A Lahiri, Goutam Kumar.
%D 2015
%J Inorganic Chemistry
%K acetylacetonate benzoquinonediimine bipyridine complex complex;DFT complex;ruthenium crystal electrochem electron phenylazopyridine prepn;spectroelectrochem ruthenium structure transition
%N 7
%P 3376--3386
%R 10.1021/ic503070j
%T 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
%V 54
%X The compds. Ru(acac)2(Q) (1), Ru(bpy)2(Q)(ClO4)2 (2(ClO4)2), and Ru(pap)2(Q)PF6 (3PF6), contg. Q = N,N'-diphenyl-o-benzoquinonediimine and donating 2,4-pentanedionate ligands (acac-), p-accepting 2,2'-bipyridine (bpy), or strongly p-accepting 2-phenylazopyridine (pap) were prepd. and structurally identified. The electronic structures of the complexes and several accessible oxidized and reduced forms were studied exptl. (electrochem., magnetic resonance, UV-visible-near-IR (UV-visible-NIR) spectroelectrochem.) 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 oxidn. states Q0-Q2- of the noninnocent ligand, the series 22+-20 and 32+-3- retain RuII. The bpy and pap co-ligands are not only spectators but can also be reduced prior to a second redn. of Q. The present study with new exptl. 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 oxidn. state formulation RuII(Q0) or RuIII(Q.bul.-). on SciFinder(R)
@article{Das.2015,
abstract = {The compds. Ru(acac)2(Q) (1), [Ru(bpy)2(Q)](ClO4)2 ([2](ClO4)2), and [Ru(pap)2(Q)]PF6 ([3]PF6), contg. Q = N,N'-diphenyl-o-benzoquinonediimine and donating 2,4-pentanedionate ligands (acac-), \textgreek{p}-accepting 2,2'-bipyridine (bpy), or strongly \textgreek{p}-accepting 2-phenylazopyridine (pap) were prepd. and structurally identified. The electronic structures of the complexes and several accessible oxidized and reduced forms were studied exptl. (electrochem., magnetic resonance, UV-visible-near-IR (UV-visible-NIR) spectroelectrochem.) 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 oxidn. states Q0-Q2- of the noninnocent ligand, the series 22+-20 and 32+-3- retain RuII. The bpy and pap co-ligands are not only spectators but can also be reduced prior to a second redn. of Q. The present study with new exptl. 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 oxidn. state formulation RuII(Q0) or RuIII(Q.bul.-). [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Das, Ankita and Ghosh, Prabir and Plebst, Sebastian and Schwederski, Brigitte and Mobin, Shaikh M. and Kaim, Wolfgang and Lahiri, Goutam Kumar.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2ece38f114d3a4a932bee6b85b3f708b6/b_schwederski},
doi = {10.1021/ic503070j},
interhash = {fc0513e26779fa133727a05d7cbf2f9a},
intrahash = {ece38f114d3a4a932bee6b85b3f708b6},
issn = {0020-1669},
journal = {Inorganic Chemistry},
keywords = {acetylacetonate benzoquinonediimine bipyridine complex complex;DFT complex;ruthenium crystal electrochem electron phenylazopyridine prepn;spectroelectrochem ruthenium structure transition},
number = 7,
pages = {3376--3386},
timestamp = {2019-07-15T11:42:10.000+0200},
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},
volume = 54,
year = 2015
}
