Pseudo-octahedral nickel(ii) complexes of strongly absorbing benzannulated pincer-type amido ligands: ligand-based redox and non-Aufbau electronic behaviour.
RSC Adv
; 11(6): 3547-3555, 2021 Jan 14.
Article
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| ID: mdl-35424319
ABSTRACT
The synthesis, structures and electronic characterization of three strongly coloured, pseudo-octahedral Ni(ii) complexes supported by redox-active diarylamido ligands featuring benzannulated N-heterocyclic donor arms are reported. The S = 1 paramagnets each present two singly occupied molecular orbitals (SOMOs) identified as metal-based by density functional theory (DFT), consistent with solid-state and solution magnetism measurements. Upon applying oxidative potentials, non-Aufbau behaviour leads to the appearance of intense and well-defined absorption features extending into the near IR (NIR). The attribution of these features to the onset of aminyl radical character through ligand-based redox is corroborated by exceptionally strong intervalence charge-transfer (IVCT) transitions ascribed to electronic communication between two Namido moieties across a Ni(ii) bridge.
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RSC Adv
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2021
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Article