Radical Localization in a Series of Symmetric NiII Complexes with Oxidized Salen Ligands

Square-planar nickel(II) complexes of salen ligands,N,N'-bis(3-tert-butyl-(5R)-salicylidene)-1,2-cyclohexanediamine), in which R = tert-butyl (1), OMe (2), and NMe2 (3), were prepared and the electronic structure of the one-electron-oxidized species [1-3](+center dot) 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(+center dot)>2(+center dot)>3(+center dot) was obtained. The cations [1-3](+center dot) 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(+center dot), whereas two distinct populations were observed for 2(+center dot). The resonance Raman spectra of 2(+center dot) and 3(+center dot) displayed the nu(8a) band of the phenoxyl radicals at 1612 cm(-1), as well as the nu(8a) bands of the phenolates. In contrast, the Raman spectrum of 1(+center dot) exhibited the nu(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(+center dot) (Delta nu(1/2) = 660 cm(-1), epsilon = 21700 M(-1)cm(-1)), indicating that the electron hole is fully delocalized over the ligand. The broader and moderately intense NIR transition of 2(+center dot) (Delta nu(1/2) = 1250 cm(-1), epsilon = 12800 M(-1)cm(-1)) suggests a certain degree of ligand-radical localization, whereas the very broad NIR transition of 3(+center dot) (Delta nu(1/2) = 8630 cm(-1), epsilon = 2550 M(-1)cm(-1)) indicates significant localization of the ligand radical on a single ring. Therefore, 1(+center dot) is a Class III mixed-valence complex, 2(+center dot) is Class II/III borderline complex, and 3(+center dot) 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.