Zero-field splitting in a series of structurally related mononuclear NiII-bispidine complexes

• Verfasst von: Atanasov, Mihail [VerfasserIn]
• Verfasst von: Comba, Peter [VerfasserIn]
• Verfasst von: Helmle, Stefan [VerfasserIn]
• Verfasst von: Müller, Dennis [VerfasserIn]
• Titel: Zero-field splitting in a series of structurally related mononuclear NiII-bispidine complexes
• Verf.angabe: Mihail Atanasov, Peter Comba, Stefan Helmle, Dennis Müller, and Frank Neese
• Umfang: 12 S.
• Fussnoten: Im Titel ist "II" hochgestellt ; Gesehen am 20.08.2018
• Titel Quelle: Enthalten in: Inorganic chemistry
• Jahr Quelle: 2012
• Band/Heft Quelle: 51(2012), 22, S. 12324-12335
• ISSN Quelle: 1520-510X
• DOI: doi:10.1021/ic3016047
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1580198872

Abstract

The synthesis, single-crystal X-ray structures, electronic absorption spectra, and magnetic properties of six NiII complexes with a tetradentate (L1) and three pentadentate (L2, L3, L4) bispidine ligands (3,7-diazabicyclo[3.3.1]nonane derivatives), Ni(L1·H2O)(OH2)2](PF6)2, [Ni(L1·H2O)(O2NO)]NO3, [Ni(L1·H2O)(OOCCH3)]PF6, [Ni(L2·H2O)NCMe](PF6)2, [Ni(L3·H2O)OH2](PF6)2, and [Ni(L4·H2O)NCMe](PF6)2 are reported. The Ni-donor bonding to pyridine and tertiary amine groups and oxygen- or nitrogen-bound coligands, completing the octahedral coordination sphere of NiII, is analyzed using a combination of ab initio electronic structure calculations (complete active space self-consistent field, CASSCF, followed by N-electron valence perturbation theory, NEVPT2) and angular overlap ligand field analysis. Magnetic properties are rationalized with an analysis of the magnetic anisotropy in terms of zero-field splitting and g-tensor parameters, obtained from first principles, and their correlation with the NiII-donor bonding parameters from the ligand field analysis of the ab initio results. A two-dimensional spectrochemical series of the ligands considered, according to their σ and π bonding to NiII, is also derived.