The First Conducting Spin-Crossover Compound Combining a MnIII Cation Complex with Electroactive TCNQ Demonstrating an Abrupt Spin Transition with a Hysteresis of 50†K.

We present herein the synthesis, crystal structure, and electric and magnetic properties of the spin-crossover salt [Mn(5-Cl-sal-N-1,5,8,12)]TCNQ1.5 ⋅2 CH3 CN (I), where 5-Cl-sal-N-1,5,8,12=N,N'-bis(3-(2-oxy-5-chlorobenzylideneamino)propyl)-ethylenediamine, containing distinct conductive and magnetic blocks along with acetonitrile solvent molecules. The MnIII complex with a Schiff-base ligand, [Mn(5-Cl-sal-N-1,5,8,12)]+ , acts as the magnetic unit, and the π-electron acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ- ) is the conducting unit. The title compound (I) exhibits semiconducting behavior with room temperature conductivity σRT ≈1×10-4  ohm-1 cm-1 and activation energy Δ ≈0.20 eV. In the temperature range 73-123 K, it experiences a hysteretic phase transition accompanied by a crossover between the low-spin S=1 and high-spin S=2 states of MnIII and changes in bond lengths within the MnN4 O2 octahedra. The pronounced shrinkage of the basal Mn-N bonds in I at the spin crossover suggests that the d x 2 - y 2 orbital is occupied/deoccupied in this transition. Interestingly, the bromo isomorphic counterpart [Mn(5-Br-sal-N-1,5,8,12)]TCNQ1.5 ⋅2 CH3 CN (II) of the title compound evidences no spin-crossover phenomena and remains in the high-spin state in the temperature range 2-300 K. Comparison of the chloro and bromo compounds allows the thermal and spin-crossover contributions to the overall variation in bond lengths to be distinguished. The difference in magnetic behavior of these two salts has been ascribed to intermolecular supramolecular effects on the spin transition. Discrete hydrogen bonding exists between cations and cations and anions in both compounds. However, the hydrogen bonding in the crystals of II is much stronger than in I. The relatively close packing arrangement of the [Mn(5-Br-sal-N-1,5,8,12)]+ cations probably precludes their spin transformation.

Evidence of field induced slow magnetic relaxation in cis-[Co(hfac)2(H2O)2] exhibiting tri-axial anisotropy with a negative axial component.

We report a combined experimental characterization and theoretical modeling of the hexa-coordinated high-spin Co(ii) complex cis-[Co(hfac)2(H2O)2] (I). The magnetic static field (DC) data and EPR spectra (measurements were carried out on the powder samples of diluted samples cis-[Co0.02Zn0.98 (hfac)2(H2O)2]) were analyzed with the aid of the parametric Griffith Hamiltonian for the high-spin Co(ii) supported by the ab initio calculations of the crystal field (CF) parameters, g-factors and superexchange parameters between H-bonded Co(ii) ions in the neighboring molecules in a 1D network. This analysis suggests the presence of the easy axis of magnetic anisotropy and also shows the existence of a significant rhombic component. The detected frequency dependent (AC) susceptibility signal shows that complex I exhibits slow paramagnetic relaxation in the applied DC field belonging thus to the class of non-uniaxial field induced single ion magnets with a negative axial component of anisotropy. It is demonstrated that the main contributions to the relaxation come from the direct one-phonon process dominating at low temperatures, while the contribution of the two-phonon Raman process becomes important with increasing temperature.

Single-Ion Magnet Et4N[CoII(hfac)3] with Nonuniaxial Anisotropy: Synthesis, Experimental Characterization, and Theoretical Modeling.

In this article we report the synthesis and structure of the new Co(II) complex Et4N[CoII(hfac)3] (I) (hfac = hexafluoroacetylacetonate) exhibiting single-ion magnet (SIM) behavior. The performed analysis of the magnetic characteristics based on the complementary experimental techniques such as static and dynamic magnetic measurements, electron paramagnetic resonance spectroscopy in conjunction with the theoretical modeling (parametric Hamiltonian and ab initio calculations) demonstrates that the SIM properties of I arise from the nonuniaxial magnetic anisotropy with strong positive axial and significant rhombic contributions.

Singularity of proton transport in salts of orthoperiodic and orthotellurium acids: theoretical modeling using density functional calculations.

Density functional B3LYP calculations have been performed to investigate proton transport in orthoperiodic and orthotellurium acids, their salts MIO(6)H(4)(M = Li, Rb, Cs) and CsH(5)TeO(6), dimers of the salt*acid type MIO(6)H(4)*H(5)IO(6)(M = Rb, Cs), CsIO(6)H(4)*H(6)TeO(6), CsHSO(4)*H(6)TeO(6), Cs(2)SO(4)*H(6)TeO(6), and also in double-substituted and binary salts Rb(2)H(3)IO(6) and Rb(4)H(2)I(2)O(10). It has been shown that the energy of salt dimerization is 33-35 kcal mol(-1) and the activation barrier for proton migration between the neighboring octahedrons of the salt*acid --> acid*salt type is calculated to be 3-13 kcal mol(-1). The activation energy of the proton migration along the octahedron, 20-30 kcal mol(-1), is comparable with the barrier for water molecule separation. Quantum-chemical calculations correlate with the results of X-ray and electrochemical studies.