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Radical localization in a series of symmetric Ni(II) complexes with oxidized salen ligands.

Square‐planar nickel(II) complexes of salen ligands, ,′‐bis(3‐‐butyl‐(5)‐salicylidene)‐1,2‐cyclohexanediamine), in which R=‐butyl (), OMe (), and NMe (), were prepared and the electronic structure of the one‐electron‐oxidized species [–] was investigated in solution. Cyclic voltammograms of [–] show... Full description

Journal Title: Chemistry (Weinheim an der Bergstrasse Germany), October 29, 2012, Vol.18(44), pp.14117-14127
Main Author: Chiang, Linus
Other Authors: Kochem, Amélie , Jarjayes, Olivier , Dunn, Tim J , Vezin, Hervé , Sakaguchi, Miyuki , Ogura, Takashi , Orio, Maylis , Shimazaki, Yuichi , Thomas, Fabrice , Storr, Tim
Format: Electronic Article Electronic Article
Language: English
Subjects:
ID: E-ISSN: 1521-3765 ; DOI: 10.1002/chem.201201410
Link: http://search.proquest.com/docview/1114705389/?pq-origsite=primo
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title: Radical localization in a series of symmetric Ni(II) complexes with oxidized salen ligands.
format: Article
creator:
  • Chiang, Linus
  • Kochem, Amélie
  • Jarjayes, Olivier
  • Dunn, Tim J
  • Vezin, Hervé
  • Sakaguchi, Miyuki
  • Ogura, Takashi
  • Orio, Maylis
  • Shimazaki, Yuichi
  • Thomas, Fabrice
  • Storr, Tim
subjects:
  • Coordination Complexes–Chemistry
  • Electron Spin Resonance Spectroscopy–Chemistry
  • Ethylenediamines–Chemistry
  • Ions–Chemistry
  • Ligands–Chemistry
  • Nickel–Chemistry
  • Oxidation-Reduction–Chemistry
  • Coordination Complexes
  • Ethylenediamines
  • Ions
  • Ligands
  • Nickel
  • Disalicylaldehyde Ethylenediamine
ispartof: Chemistry (Weinheim an der Bergstrasse, Germany), October 29, 2012, Vol.18(44), pp.14117-14127
description: Square‐planar nickel(II) complexes of salen ligands, ,′‐bis(3‐‐butyl‐(5)‐salicylidene)‐1,2‐cyclohexanediamine), in which R=‐butyl (), OMe (), and NMe (), were prepared and the electronic structure of the one‐electron‐oxidized species [–] was investigated in solution. Cyclic voltammograms of [–] showed two quasi‐reversible redox waves that were assigned to the oxidation of the phenolate moieties to phenoxyl radicals. From the difference between the first and second redox potentials, the trend of electronic delocalization >> was obtained. The cations [–] exhibited isotropic tensors of 2.045, 2.023, and 2.005, respectively, reflecting a lower metal character of the singly occupied molecular orbital (SOMO) for systems that involve strongly electron‐donating substituents. Pulsed‐EPR spectroscopy showed a single population of equivalent imino nitrogen atoms for , whereas two distinct populations were observed for . The resonance Raman spectra of and displayed the ν band of the phenoxyl radicals at 1612 cm, as well as the bands of the phenolates. In contrast, the Raman spectrum of exhibited the band at 1602 cm, without any evidence of the phenolate peak. Previous work showed an intense near‐infrared (NIR) electronic transition for (Δ=660 cm, =21 700  cm), indicating that the electron hole is fully delocalized over the ligand. The broader and moderately intense NIR transition of (Δ=1250 cm, =12 800  cm) suggests a certain degree of ligand‐radical localization, whereas the very broad NIR transition of (Δ=8630 cm, =2550  cm) indicates significant localization of the ligand radical on a single ring. Therefore, is a Class III mixed‐valence complex, is Class II/III borderline complex, and is a Class II complex according to the Robin–Day classification method. By employing the Coulomb‐attenuated method (CAM‐B3LYP) we were able to predict the electron‐hole localization and NIR transitions in the series, and show that the energy match between the redox‐active ligand and the metal d orbitals is crucial for delocalization of the radical SOMO. Square planar, symmetric nickel(II) complexes of salen ligands with different substituents on the ring were prepared, and the electronic structures of the one‐electron‐oxidized species were investigated. Increasing the electron‐donating ability of the substituents led to localization of the ligand radical (see figure).
language: eng
source:
identifier: E-ISSN: 1521-3765 ; DOI: 10.1002/chem.201201410
fulltext: fulltext
issn:
  • 15213765
  • 1521-3765
url: Link


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titleRadical localization in a series of symmetric Ni(II) complexes with oxidized salen ligands.
creatorChiang, Linus ; Kochem, Amélie ; Jarjayes, Olivier ; Dunn, Tim J ; Vezin, Hervé ; Sakaguchi, Miyuki ; Ogura, Takashi ; Orio, Maylis ; Shimazaki, Yuichi ; Thomas, Fabrice ; Storr, Tim
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ispartofChemistry (Weinheim an der Bergstrasse, Germany), October 29, 2012, Vol.18(44), pp.14117-14127
identifierE-ISSN: 1521-3765 ; DOI: 10.1002/chem.201201410
subjectCoordination Complexes–Chemistry ; Electron Spin Resonance Spectroscopy–Chemistry ; Ethylenediamines–Chemistry ; Ions–Chemistry ; Ligands–Chemistry ; Nickel–Chemistry ; Oxidation-Reduction–Chemistry ; Coordination Complexes ; Ethylenediamines ; Ions ; Ligands ; Nickel ; Disalicylaldehyde Ethylenediamine
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descriptionSquare‐planar nickel(II) complexes of salen ligands, ,′‐bis(3‐‐butyl‐(5)‐salicylidene)‐1,2‐cyclohexanediamine), in which R=‐butyl (), OMe (), and NMe (), were prepared and the electronic structure of the one‐electron‐oxidized species [–] was investigated in solution. Cyclic voltammograms of [–] showed two quasi‐reversible redox waves that were assigned to the oxidation of the phenolate moieties to phenoxyl radicals. From the difference between the first and second redox potentials, the trend of electronic delocalization >> was obtained. The cations [–] exhibited isotropic tensors of 2.045, 2.023, and 2.005, respectively, reflecting a lower metal character of the singly occupied molecular orbital (SOMO) for systems that involve strongly electron‐donating substituents. Pulsed‐EPR spectroscopy showed a single population of equivalent imino nitrogen atoms for , whereas two distinct populations were observed for . The resonance Raman spectra of and displayed the ν band of the phenoxyl radicals at 1612 cm, as well as the bands of the phenolates. In contrast, the Raman spectrum of exhibited the band at 1602 cm, without any evidence of the phenolate peak. Previous work showed an intense near‐infrared (NIR) electronic transition for (Δ=660 cm, =21 700  cm), indicating that the electron hole is fully delocalized over the ligand. The broader and moderately intense NIR transition of (Δ=1250 cm, =12 800  cm) suggests a certain degree of ligand‐radical localization, whereas the very broad NIR transition of (Δ=8630 cm, =2550  cm) indicates significant localization of the ligand radical on a single ring. Therefore, is a Class III mixed‐valence complex, is Class II/III borderline complex, and is a Class II complex according to the Robin–Day classification method. By employing the Coulomb‐attenuated method (CAM‐B3LYP) we were able to predict the electron‐hole localization and NIR transitions in the series, and show that the energy match between the redox‐active ligand and the metal d orbitals is crucial for delocalization of the radical SOMO. Square planar, symmetric nickel(II) complexes of salen ligands with different substituents on the ring were prepared, and the electronic structures of the one‐electron‐oxidized species were investigated. Increasing the electron‐donating ability of the substituents led to localization of the ligand radical (see figure).
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titleRadical localization in a series of symmetric Ni(II) complexes with oxidized salen ligands.
authorChiang, Linus ; Kochem, Amélie ; Jarjayes, Olivier ; Dunn, Tim J ; Vezin, Hervé ; Sakaguchi, Miyuki ; Ogura, Takashi ; Orio, Maylis ; Shimazaki, Yuichi ; Thomas, Fabrice ; Storr, Tim
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