期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 14, 期 4, 页码 1169-1177出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200701243
关键词
EPR spectroscopy; macrocyclic ligands; magnetic properties; N ligands; nickel
Pentacoordinate complexes in which Ni-II is chelated by the tridentate macrocyclic ligand 1,4,7-triisopropyl-1,4,7-triazacyclononane (iPrtacn) of formula [Ni(iPrtacn)X-2] (X=Cl, Br, NCS) have relatively large magnetic anisotropies, revealed by the large zero-field splitting (zfs) axial parameters vertical bar D vertical bar of around 15cm(-1) measured by frequency-domain magnetic resonance spectroscopy (FDMRS) and high-field high-frequency electron. paramagnetic resonance (HF-HFEPR). The spin Hamiltonian parameters for the three complexes were determined by analyzing the FDMRS spectra at different temperatures in zero applied magnetic field in an energy window between 0 and 40 cm(-1). The same parameters were determined from analysis of HF-HFEPR data measured at different frequencies (285, 380, and 475 GHz) and at 7 and 17 K. The spin Hamiltonian parameters D (axial) and E (rhombic) were calculated for the three complexes in the framework of the angular overlap model (AOM). The nature and magnitude of the magnetic anisotropy of the three complexes and the origin of the influence of the X atoms were analyzed by performing systematic calculations on model complexes.
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