What Controls the Magnetic Exchange and Anisotropy in a Family of Tetranuclear {Mn2IIMn2III} Single-Molecule Magnets?

© 2017 American Chemical Society.Twelve heterovalent, tetranuclear manganese(II/III) planar diamond or “butterfly” complexes, 1-12, have been synthesized and structurally characterized, and their magnetic properties have been probed using experimental and theoretical techniques. The 12 structures are divided into two distinct “classes”. Compounds 1-8 place the Mn(III), S = 2, ions in the body positions of the butterfly metallic core, while the Mn(II), S = 5/2, ions occupy the outer wing sites and are described as “Class 1”. Compounds 9-12 display the reverse arrangement of ions and are described as “Class 2”. Direct current susceptibility measurements for 1-12 reveal ground spin states ranging from S = 1 to S = 9, with each complex displaying unique magnetic exchange parameters (J). Alternating current susceptibility measurements found that that slow magnetic relaxation is observed for all complexes, except for 10 and 12, and display differing anisotropy barriers to magnetization reversal. First, we determined the magnitude of the magnetic exchange parameters for all complexes. Three exchange coupling constants (Jbb, Jwb, and Jww) were determined by DFT methods which are found to be in good agreement with the experimental fits. It was found that the orientation of the Jahn-Teller axes and the Mn-Mn distances play a pivotal role in determining the sign and strength of the Jbb parameter. Extensive magneto-structural correlations have been developed for the two classes of {MnII2MnIII2} butterfly complexes by varying the Mnb-O distance, Mnw-O distance, Mnb-O-Mnb angle (α), Mnb-O-Mnb-O dihedral angle (γ), and out-of-plane shift of the Mnw atoms (β). For the magnetic anisotropy the DFT calculations yielded larger negative D value for complexes 2, 3, 4, and 6 compared to the other complexes. This is found to be correlated to the electron-donating/withdrawing substituents attached to the ligand moiety and suggests a possible way to fine tune the magnetic anisotropy in polynuclear Mn ion complexes

New examples of triangular terbium(iii) and holmium(iii) and hexagonal dysprosium(iii) single molecule toroics

© 2019 The Royal Society of Chemistry. The structural, magnetic and theoretical aspects are described for three triangular lanthanide complexes, [TbIII3(OH)(teaH2)3(paa)3]Cl2 (1), [DyIII3(OH)(teaH2)3(paa)3]Cl2 (2) and [HoIII3(OH)(teaH2)3(paa)3]Cl2 (3), and a hexanuclear wheel of formula [DyIII6(pdeaH)6(NO3)6] (4) [teaH3 = triethanolamine, paaH = N-(2-pyridyl)-acetoacetamide and pdeaH3 = 3-[bis(2-hydroxyethyl)amino]propan-1-ol]. Each complex displays single molecule toroidal behaviour as rationalised using high-level ab initio calculations. Complexes 2 and 3 are the first examples of mixed moment single molecule toroidal complexes featuring non-Kramers ions

Rationalizing the sign and magnitude of the magnetic coupling and anisotropy in dinuclear manganese(iii) complexes

© 2018 The Royal Society of Chemistry. We have synthesised twelve manganese(iii) dinuclear complexes, 1-12, in order to understand the origin of magnetic exchange (J) between the metal centres and the magnetic anisotropy (D) of each metal ion using a combined experimental and theoretical approach. All twelve complexes contain the same bridging ligand environment of one μ-oxo and two μ-carboxylato, that helped us to probe how the structural parameters, such as bond distance, bond angle and especially Jahn-Teller dihedral angle affect the magnetic behaviour. Among the twelve complexes, we found ferromagnetic coupling for five and antiferromagnetic coupling for seven. DFT computed the J and ab initio methods computed the D parameter, and are in general agreement with the experimentally determined values. The dihedral angle between the two Jahn-Teller axes of the constituent MnIII ions are found to play a key role in determining the sign of the magnetic coupling. Magneto-structural correlations are developed by varying the Mn-O distance and the Mn-O-Mn angle to understand how the magnetic coupling changes upon these structural changes. Among the developed correlations, the Mn-O distance is found to be the most sensitive parameter that switches the sign of the magnetic coupling from negative to positive. The single-ion zero-field splitting of the MnIII centres is found to be negative for complexes 1-11 and positive for complex 12. However, the zero-field splitting of the S = 4 state for the ferromagnetic coupled dimers is found to be positive, revealing a significant contribution from the exchange anisotropy-a parameter which has long been ignored as being too small to be effective

Observation of Ferromagnetic Exchange, Spin Crossover, Reductively Induced Oxidation, and Field-Induced Slow Magnetic Relaxation in Monomeric Cobalt Nitroxides

The reaction of [Co-II(NO3)(2)]center dot 6H(2)O with the nitroxide radical, 4-dimethyl-2,2-di(2-pyridyl) oxazolidine-N-oxide (L-center dot), produces the mononuclear transition-metal complex [Co-II(L-center dot)(2)](NO3)(2) (1), which has been investigated using temperature-dependent magnetic susceptibility, electron paramagnetic resonance (EPR) spectroscopy, electrochemistry, density functional theory (DFT) calculations, and variable-temperature X-ray structure analysis. Magnetic susceptibility measurements and X-ray diffraction (XRD) 'analysis reveal a central low-spin octahedral Co2+ ion with both ligands in the neutral radical form (L-center dot) forming a linear L-center dot center dot center dot center dot Co(II)center dot center dot center dot L-center dot arrangement. This shows a host of interesting magnetic properties including strong cobalt-radical and radical-radical intramolecular ferromagnetic interactions stabilizing a S = 3/2 ground state, a thermally induced spin crossover transition above 200 K and field-induced slow magnetic relaxation. This is supported by variable-temperature EPR spectra, which suggest that 1 has a positive D value and nonzero E values, suggesting the possibility of a field-induced transverse anisotropy barrier. DFT calculations support the parallel alignment of the two radical pi*No orbitals with a small orbital overlap leading to radical-radical ferromagnetic interactions while the cobalt-radical interaction is computed to be strong and ferromagnetic. In the high-spin (HS) case, the DFT calculations predict a weak antiferrornagnetic cobalt-radical interaction, whereas the radical-radical interaction is computed to be large and ferromagnetic. The monocationic complex [Co-III(L-)(2)](BPh4) (2) is formed by a rare, reductively induced oxidation of the Co center and has been fully characterized by X-ray structure analysis and magnetic measurements revealing a diamagnetic ground state. Electrochemical studies on 1 and 2 revealed common Co-redox intermediates and the proposed mechanism is compared and contrasted with that of the Fe analogues