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Two seven-coordinate Co(II)-nitrate complexes, [Co(tmpdc)(NO3)2] (1) and [Co(tmpdt)(NO3)2]·CH3CN (2) (tmpdc = N,N,N′,N′-tetramethyl-2,6-pyridinedicarboxamide, tmpdt = N,N,N′,N′-tetramethyl-2,6-pyridinedithiocarboxamide) with tridentate neutral ligands tmpdc or tmpdt have been prepared. Their crystal structures by single X-ray diffraction show markedly different coordination geometries when two donor atoms of the tridentate ligand change from oxygen in 1 to sulfur in 2. Complex 1 is a capped octahedral while complex 2 is a pentagonal bipyramid. Results of direct-current (dc) magnetic measurements and high-frequency electron paramagnetic resonance (HFEPR) indicate the anisotropic S = 3/2 spin ground state of the Co(II) ions with the easy-plane anisotropy for both 1 and 2. Frequency- and temperature-dependent alternating-current (ac) magnetic susceptibility studies reveal slow magnetic relaxation for 1 and 2 under applied fields. [ABSTRACT FROM AUTHOR]

Cyclic 3d-4f molecular magnets have received considerable attention owing to their potential applications in high-density data storage and quantum information processing. As a rare example of ferromagnetic polynuclear Cr rings, {Cr8Y8} represents a valuable test bed to directly study the magnetic interaction between Cr3+ ions in large hexadecametallic {Cr8Ln8} (Ln = 4f metal) molecules. We have proposed a "single-J" model to approximate the low-temperature spin dynamics of {Cr8Y8} in our earlier study, while a zero-field splitting (ZFS) of the quantum levels was also suggested by the heat capacity data. In order to have a deeper understanding of the magnetism of {Cr8Y8}, it is necessary to verify the ZFS by means of high-resolution spectral methods and identify its origin. In this work, we present a high-frequency electron spin resonance (HF-ESR) study on the ZFS of {Cr8Y8}. The X-band ESR spectra consists of multi-peak structure, indicative of magnetic anisotropy that breaks the degeneracy between spin states in the absence of a magnetic field. HF-ESR spectra are collected to extract the ZFS parameters. We observed a sharp resonance peak due to the transitions between the S = 11 quantum levels and a broadband corresponding to a distribution of resonance peaks due to the ZFS of the S = 12 quantum levels. By analyzing HF-ESR spectra, we confirm the expected S = 12 ground state and determine its ZFS parameter D as −0.069 K, and, furthermore, we reproduce the spectra recorded at 154 GHz. The macrospin model proves to still be valid. The ZFS is attributed to the axial magnetic anisotropy, as found in some other Cr-based molecular wheels. The detailed HF-ESR investigation presented in this paper will benefit the studies on other {Cr8Ln8} wheels with magnetic Ln3+ ions and highlights the importance of the HF-ESR method as a high-resolution probe in determining the ZFS parameters with very small magnitude. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Precise modulation of the magnetic anisotropy of metal ions remains highly important for the development of high–performance single‐molecule magnets (SMMs). We herein reported the synthetic, structural, spectral, magnetic, and computational studies on four mononuclear CoII complexes in a distorted octahedral environment. The change of the organosulfonate anions triggers significant modification of the distorted octahedral CoN6 coordination sphere, which enables us to tackle the influence of the structural distortion on the magnetic anisotropy in these complexes. Magnetic measurements revealed that the four complexes possess easy–plane magnetic anisotropy with large and positive zero‐field splitting parameters, which decrease with the increasing distortion of the pseudo–octahedral CoII coordination geometry. This correlation was further confirmed by high–frequency/–field EPR (HF–EPR) spectra and theoretical calculations. Dynamic magnetic susceptibility measurements indicate that these complexes both exhibit slow magnetic relaxation under an external dc field, indicating the field‐induced single‐ion magnets (SIMs) of the four complexes. These results indicate that structural distortion plays an important role in the magnetic anisotropy of CoII complexes and should be carefully considered in the design of molecular complexes with high magnetic anisotropy. [ABSTRACT FROM AUTHOR]

Three mononuclear tetrakis(pseudohalido)-cobalt(II) complexes (Ph4P)2[Co(E)4] (E = N3−, 1; NCO−, 2; NCS−, 3) have been synthesized and structurally characterized. Each compound contains a distorted tetrahedral Co2+ ion coordinated by four pseudohalide ligands. The magnetic properties of 1–3 have been studied using direct-current magnetic measurements and high-frequency and -field EPR spectroscopy (HFEPR), suggesting easy-axis magnetic anisotropy for 1 and 2 and easy-plane anisotropy for 3. Analysis of the HFEPR spectra yielded D values of −5.23 and +3.63 cm−1 for 2 and 3, respectively. The absence of the EPR signal in 1 is consistent with a large, negative value of the zero-field splitting (ZFS) parameter D in 1. The nature of magnetic anisotropies of 1–3 has also been confirmed by ab initio calculations. The calculated D values are consistent with those determined using magnetometry and HFEPR studies. Alternating current (AC) magnetic susceptibilities reveal slow magnetic relaxation under an applied magnetic field, thus indicating that 1–3 are field-induced single-ion magnets (SIMs). [ABSTRACT FROM AUTHOR]