Zero-field splitting in metal complexes

Boča, Roman

doi:10.1016/j.ccr.2004.03.001

Cited by 833 publications

(569 citation statements)

References 208 publications

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“…All the calculated values of g iso show a positive deviation from the free-electron g-value as expected for TM ions with a more-than-half-filled 3d shell. The results reflect the trends expected based on the electronic structure of the involved ions [45,79]. The deviation from g e is found to be negligible for Mn 2+ as it has zero spin-orbit coupling as a result of the half-filled 3d shell.…”

Section: Resultssupporting

confidence: 87%

DFT investigation of the effect of spin-orbit coupling on the NMR shifts in paramagnetic solids

et al. 2017

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Nuclear Magnetic Resonance (NMR) spectroscopy is a powerful tool for studying the structural and electronic properties of paramagnetic solids. However, the interpretation of paramagnetic NMR spectra is often challenging as a result of the interactions of unpaired electrons with the nuclear spins of interest. In this work, we extend the formalism of the paramagnetic NMR shielding in the presence of spin-orbit coupling towards solid systems with multiple paramagnetic centres. We demonstrate how the single-ion Electron Paramagnetic Resonance (EPR) g-tensor is defined and calculated in periodic paramagnetic solids. We then calculate the hyperfine tensor and the g-tensor with density functional theory (DFT) to show the validity of the presented model and we further demonstrate how these interactions can be combined to give the overall paramagnetic shielding tensor, σ s . The method is applied to a series of olivine-type LiTMPO4 materials (with TM=Mn, Fe, Co and Ni) and the corresponding 7 Li and 31 P NMR spectra are simulated. We analyse the effects of spin-orbit coupling and of the electron-nuclear magnetic interactions on the calculated NMR parameters. A detailed comparison is presented between contact and dipolar interactions across the LiTMPO4 series, in which the magnitudes and signs of the non-relativistic and relativistic components of the overall isotropic shift and shift anisotropy are computed and rationalized.

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Section: Resultssupporting

confidence: 87%

DFT investigation of the effect of spin-orbit coupling on the NMR shifts in paramagnetic solids

et al. 2017

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“…The octahedral coordination of Mn(II) ions is completed with two chloride ions in cis. This type of structure has been found for other oxalate-based [169] and homometallic anilate-based compounds [7,170,171], but it is the first time that it is obtained for heterometallic anilate-based networks (Figure 23). 3 ] − lattice, independently of the inserted cation.…”

Section: Spin-crossover Complexessupporting

confidence: 61%

Recent Advances on Anilato-Based Molecular Materials with Magnetic and/or Conducting Properties

et al. 2017

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Abstract:The aim of the present work is to highlight the unique role of anilato-ligands, derivatives of the 2,5-dioxy-1,4-benzoquinone framework containing various substituents at the 3 and 6 positions (X = H, Cl, Br, I, CN, etc.), in engineering a great variety of new materials showing peculiar magnetic and/or conducting properties. Homoleptic anilato-based molecular building blocks and related materials will be discussed. Selected examples of such materials, spanning from graphene-related layered magnetic materials to intercalated supramolecular arrays, ferromagnetic 3D monometallic lanthanoid assemblies, multifunctional materials with coexistence of magnetic/conducting properties and/or chirality and multifunctional metal-organic frameworks (MOFs) will be discussed herein. The influence of (i) the electronic nature of the X substituents and (ii) intermolecular interactions i.e., H-Bonding, Halogen-Bonding, π-π stacking and dipolar interactions, on the physical properties of the resulting material will be also highlighted. A combined structural/physical properties analysis will be reported to provide an effective tool for designing novel anilate-based supramolecular architectures showing improved and/or novel physical properties. The role of the molecular approach in this context is pointed out as well, since it enables the chemical design of the molecular building blocks being suitable for self-assembly to form supramolecular structures with the desired interactions and physical properties.Keywords: benzoquinone derivatives; molecular magnetism; multifunctional molecular materials; spin-crossover materials; metal-organic frameworks General IntroductionThe aim of the present work is to highlight the key role of anilates in engineering new materials with new or improved magnetic and/or conducting properties and new technological applications. Only homoleptic anilato-based molecular building blocks and related materials will be discussed. Selected examples of para-/ferri-/ferro-magnetic, spin-crossover and conducting/magnetic multifunctional materials and MOFs based on transition metal complexes of anilato-derivatives, on varying the substituents at the 3,6 positions of the anilato moiety, will be discussed herein, whose structural features or physical properties are peculiar and/or unusual with respect to analogous compounds reported in the literature up to now. Their most appealing technological applications will be also reported.

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“…This value is within the normal range found for other Fe(II) complexes [32] and may include a weak antiferromagnetic interaction through the π-π interactions observed between the Fe(II) monomers. Note that the sign of D cannot be determined from powder susceptibility measurements.…”

Section: Magnetic Propertiessupporting

confidence: 84%

“…This model reproduces very satisfactorily the magnetic properties in the whole temperature range with g = 2.033(1) and |D| = 5.7(1), K = 4.0(1) cm −1 (solid line in Figure 5). This value is within the normal range found for other Fe(II) complexes [32] and may include a weak antiferromagnetic interaction through the π-π interactions observed between the Fe(II) monomers. Note that the sign of D cannot be determined from powder susceptibility measurements.…”

Section: Magnetic Propertiessupporting

confidence: 84%