Search Results (4)

Transition metal (II) complexes stabilized by 2,6-di(pyrazol-3-yl)pyridine as a novel coplanar tridentate nitrogen-donor ligand have been reported for their unusual structures and photoluminescent properties. In this work, the ligand 2,6-bis(5-isopropyl-1H-pyrazole-3-yl)pyridine (denoted as L) and its transition metal (II) halogenido complexes viz [ZnCl₂(L)] (1), [ZnBr₂(L)] (2), [CuCl₂(L)] (3), and [CuCl(L)(thf)](PF₆) (4) were synthesized and characterized by single crystal X-ray crystal analysis. Its structures contained N–H groups in its pyrazole rings and hydrogen bonds between these N–H donors and the coordinated halogenide ions and lattice solvent molecules. Tautomers between 3-pyridyl and 5-pyridyl substitutes were also observed. In L, the N–H group at the pyrazole nitrogen was located adjacent to the pyridine ring to form hydrogen bonds with adjacent pyrazoles. However, on complexation, the H atoms at the pyrazole nitrogens are shifted remotely to the pyridine. The zinc (II) complexes [ZnCl₂(L)] (1) and [ZnBr₂(L)] (2) possessed distorted trigonal pyramidal structures in the solid state. By comparison, the copper (II) complexes [CuCl₂(L)] (3) and [CuCl(L)(thf)](PF₆) (4) adopted square pyramidal geometry with a Jahn–Teller distortion resulting from their d⁹ electron configurations. Full article

Layered magnetic metal-organic frameworks (MOFs) are an emerging class of materials that can combine the advantages of both MOFs and 2D magnetic crystals. The recent discovery of large coercivity and long-range magnetic ordering up to 515 K in a layered MOF of general formula MCl₂(pyz)₂ (M = transition metal, pyz = pyrazine) offers an exciting versatile platform to achieve high-T_C magnetism at the 2D limit. In this work, we investigate the exfoliation feasibility down to the monolayer of VCl₂(pyz)₂ and CrCl₂(pyz)₂ by means of first-principles calculations. We explore their structural, electronic, magnetic and vibrational properties, as well as the effect of halide substitution. Then, we provide a full analysis of the spin-phonon coupling (SPC) in both 2D derivatives. Our calculations reveal a low SPC and thermal evolution of the magnetic exchange interactions and single-ion anisotropy mainly governed by low-frequency phonon modes. Finally, we provide chemical insights to improve the performance of these magnetic 2D MOFs based on the effective manipulation of the phonon modes that can present a major impact on their magnetic properties. Full article

The capability of a given substance to change its spin state by the action of a stimulus, such as a change in temperature, is by itself a very challenging property. Its interest is increased by the potential applications and the need to find sustainable functional materials. 3D transition metal complexes, mainly with octahedral geometry, display this property when coordinated to particular sets of ligands. The prediction of this behavior has been attempted by many authors. It is, however, made very difficult because spin crossover (SCO), as it is called, occurs most often in the solid state, where besides complexes, counter ions, and solvents are also present in many cases. Intermolecular interactions definitely play a major role in SCO. In this review, we decided to analyze SCO in mono- and binuclear transition metal complexes containing halogens as ligands or as substituents of the ligands. The aim was to try and find trends in the properties which might be correlated to halogen substitution patterns. Besides a revision of the properties, we analyzed structures and other information. We also tried to build a simple model to run Density Functional Theory (DFT) calculations and calculate several parameters hoping to find correlations between calculated indices and SCO data. Although there are many experimental studies and single-crystal X-ray diffraction structures, there are only few examples with the F, Cl, Br and series. When their intermolecular interactions were not very different, T_1/2 (temperature with 50% high spin and 50% low spin states) usually increased with the calculated ligand field parameter (Δ_oct) within a given family. A way to predict SCO remains elusive. Full article

The dithiooxalato-bridged iron mixed-valence complex (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] (dto = dithiooxalato) undergoes a novel charge-transfer phase transition (CTPT) accompanied by electron transfer between adjacent Fe^II and Fe^III sites. The CTPT influences the ferromagnetic transition temperature according to the change of spin configuration on the iron sites. To reveal the mechanism of the CTPT, we have synthesized the series of metal-substituted complexes (n-C₃H₇)₄N[Fe^II_1-xMn^II_xFe^III(dto)₃] (x = 0–1) and investigated their physical properties by means of magnetic susceptibility and dielectric constant measurements. With increasing Mn^II concentration, x, Mn^II-substituted complexes show the disappearance of CTPT above x = 0.04, while the ferromagnetic phase remains in the whole range of x. These results are quite different from the physical properties of the Zn^II-substituted complex, (n-C₃H₇)₄N[Fe^II_1-xZn^II_xFe^III(dto)₃], which is attributed to the difference of ion radius as well as the spin states of Mn^II and Zn^II. Full article