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Radical Localization in a Series of Symmetric Ni II Complexes with Oxidized Salen Ligands
Author(s) -
Chiang Linus,
Kochem Amélie,
Jarjayes Olivier,
Dunn Tim J.,
Vezin Hervé,
Sakaguchi Miyuki,
Ogura Takashi,
Orio Maylis,
Shimazaki Yuichi,
Thomas Fabrice,
Storr Tim
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201201410
Subject(s) - delocalized electron , chemistry , electron paramagnetic resonance , radical , raman spectroscopy , ligand (biochemistry) , crystallography , nickel , homo/lumo , resonance (particle physics) , redox , resonance raman spectroscopy , photochemistry , nuclear magnetic resonance , molecule , inorganic chemistry , organic chemistry , biochemistry , physics , receptor , particle physics , optics
Square‐planar nickel(II) complexes of salen ligands, N , N ′‐bis(3‐ tert ‐butyl‐(5 R )‐salicylidene)‐1,2‐cyclohexanediamine), in which R= tert ‐butyl ( 1 ), OMe ( 2 ), and NMe 2 ( 3 ), were prepared and the electronic structure of the one‐electron‐oxidized species [ 1 – 3 ] +. was investigated in solution. Cyclic voltammograms of [ 1 – 3 ] 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 1 +. > 2 +. > 3 +. was obtained. The cations [ 1 – 3 ] +. exhibited isotropic g 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 1 +. , whereas two distinct populations were observed for 2 +. . The resonance Raman spectra of 2 +. and 3 +. displayed the ν 8a band of the phenoxyl radicals at 1612 cm −1 , as well as the ν 8a bands of the phenolates. In contrast, the Raman spectrum of 1 +. exhibited the ν 8a band at 1602 cm −1 , without any evidence of the phenolate peak. Previous work showed an intense near‐infrared (NIR) electronic transition for 1 +. (Δ ν 1/2 =660 cm −1 , ε =21 700 M −1 cm −1 ), indicating that the electron hole is fully delocalized over the ligand. The broader and moderately intense NIR transition of 2 +. (Δ ν 1/2 =1250 cm −1 , ε =12 800 M −1 cm −1 ) suggests a certain degree of ligand‐radical localization, whereas the very broad NIR transition of 3 +. (Δ ν 1/2 =8630 cm −1 , ε =2550 M −1 cm −1 ) indicates significant localization of the ligand radical on a single ring. Therefore, 1 +. is a Class III mixed‐valence complex, 2 +. is Class II/III borderline complex, and 3 +. 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.