A REACTION OF 4, 5-DIPHENYLIMIDAZOLE NITRATION IN THE PRESENCE OF SOME 3D-METALS NITRATES

By interaction of cobalt(II), nickel(II), or zinc(II) nitrate with 4,5- diphenylimidazole in methanol in solvotermal conditions the new derivative of imidazole (4,5-diphenyl-2-nitroimidazole) and three new coordinative compounds [M(4,5-Ph2ImNO2)2(CH3OH)2] have been synthesized and investigated. Metal ions have a distorted octahedral environment with N2O4. Coordination number of metal is six. Ligand is coordinated to metal ion by one oxygen atom of nitrogroup and one nitrogen atom of imidazole

Intracluster interactions in butterfly {Fe3 LnO2} molecules with the non-Kramers ions Tb(III) and Ho(III)

The intracluster exchange interactions within the "butterfly" Fe3Ln(µ3-O)2(CCl3COO)8(H2O)(THF)3] molecules, where Ln(III) represents a lanthanide cation, have been determined by a combination of x-ray magnetic circular dichroism (XMCD) and vibrating sample magnetometry (VSM) along with an interaction model. We have studied the compounds with Ln=Tb and Ho, both non-Kramers lanthanides and with high uniaxial anisotropy, and Ln=Lu(III) and Y(III) as pseudolanthanides, which supply nonmagnetic Ln reference cases. At low temperature, the three Fe atoms can be considered as a self-unit with total spin SFe3=5/2. Using the element selectivity of the XMCD magnetometry, measured at the Ln L2,3 edges, together with the VSM measurements, the local magnetization of the Ln ion and the Fe3 subcluster, as a function of the field and low temperature (T˜2.5K), has been determined separately. These results are described quantitatively in the framework of a theoretical model based on an effective spin Hamiltonian, which considers the competing effects of intracluster interactions and the external applied magnetic field. The Ln-Fe3 exchange interaction within the {Fe3LnO2} cluster has been determined to be antiferromagnetic, in both Tb and Ho compounds, with JFeTb/kB=-0.13(1)K and JFeHo/kB=-0.18(1)K, respectively. In both cases, a field-induced reorientation of the Fe3 and Ln spins from antiparallel to parallel orientation takes place at a threshold field µ0H=1.1 and 2 T, for the {Fe3TbO2} and {Fe3HoO2} compounds, respectively. By comparison with other compounds of the series with uniaxial anisotropy, it is concluded that the polarizability of the Fe3 subcluster magnetic moment decreases in the trend {Fe3YO2}¿{Fe3TbO2}¿{Fe3HoO2}¿{Fe3DyO2}, because of the increasing opposition of the exchange antiferromagnetic field caused by the Ln ion. In the Ln=Tb, Ho, and Dy, the magnetization of the whole molecule is dominated by the anisotropy of the Ln ion. The intracluster Fe3-Ln exchange interactions are very weak compared to the Ln ligand field and Fe-Fe exchange interactions

Antiferromagnetic single-chain magnet slow relaxation in the {Tb(α-fur)3}n polymer with non-Kramers ions

We report the synthesis, crystal structure and magnetic properties of a new molecular complex based on a Tb(iii) ion supported by 2-furancarboxylic molecules: {Tb(α-fur)(HO)} (α-fur = CHOCOO). Two slightly different Tb sites (A and B) exist depending on the position of one of the dangling ligands. Ab initio calculations predict that, for both sites, the magnetic ground state is highly anisotropic (g∗ = 17.8) and consists of a quasi-doublet with a small gap, well isolated from the next excited state. The α-fur ligand forms 1D polymeric chains of Tb ions of the same type (either A or B) running along the c-axis. The crystal structure is formed by the supramolecular stacking along the a-axis of 2D layers containing parallel chains of the same type. Static magnetization and heat capacity measurements show that, magnetically, the system can be modeled as an ensemble of Ising chains of non-Kramers Tb ions with effective spin S∗ = 1/2, antiferromagnetically (AF) coupled by a weak intrachain interaction (J∗/k = -0.135 K). At very low temperatures, the static susceptibility reflects the presence of a 2-4% concentration of defects in the chains. Ac susceptibility measurements at H = 0 performed down to mK temperatures have enabled us to observe the slow relaxation of magnetization through two different pathways. They are assigned to Single-Chain-Magnet (SCM) behavior in two different types of AF chains (A and B), triggered by the existence of defects breaking the chains into segments with short-range order. At temperatures below 0.1 K this mechanism is replaced by individual relaxation of the ions through direct processes. Under the application of a magnetic field the system slowly relaxes by two distinct direct processes, strongly affected by a phonon bottleneck effect.This work has been financed by MECOM Projects MAT11/23791 and MAT11/27233-C02-02, MAT2015-68204-R, MAT2014-53921-R, DGA IMANA E34 and MOLCHIP E98 Projects. Consolider Nanoselect (CSD2007-00041) and by a grant of the Ministry of National Education, CNCS – UEFISCDI, project number PN-II-ID-PCE-2012-4-0261. D. P. thanks the Alexander von Humboldt (AvH) Foundation for financial support.Peer Reviewe

Preparation and properties of a calcium(II)-based molecular chain decorated with manganese(II) butterfly-like complexes

This Open Access Article is licensed under a Creative Commons Attribution 3.0 Unported Licence.The room temperature reaction of [Mn2O2(bipy) 4](ClO4)3 (bipy = 2,2′-bipyridine) with Ca(CHCl2COO)2 in methanol produced a yellow crystalline material. The X-ray determined structure comprises of a multiple calcium(ii) carboxylate bridged chain-like structure which is decorated with [Mn(bipy) 2(OH2)]2+ subunits. The redox behaviour for the complex in H2O and MeCN is reported. In the latter solvent the oxidation of the manganese ions appears to be facilitated by the presence of the calcium ions. Magnetic susceptibility and low temperature magnetization measurements show that the Mn moment is isotropic, with g = 1.99(1) and S = 5/2, confirming it is in the 2+ oxidation state. A very weak antiferromagnetic interaction is also detected. Frequency-dependent ac measurements evidence slow magnetic relaxation of the Mn(bipy)2 units. Two relaxation mechanisms are identified: a very slow direct process and a faster one caused by the Resonant Phonon Trapping mechanism. This is the first example of field-induced single ion magnet (SIM) behavior in a mononuclear Mn(ii) complex. © 2014 The Royal Society of Chemistry.This work was mainly funded by the FP7-PEOPLE-2009-IRSES Nr. 246902 grant, and partially funded by the Spanish MINECO project MAT11/23791 and the DGA project E34 (cofunded by the Fondo Social Europeo) and the European Union FEDER.Peer Reviewe

Field-induced internal Fe and Ln spin reorientation in butterfly {Fe3LnO2} (Ln = Dy and Gd) single-molecule magnets

Under the terms of the Creative Commons Attribution License 3.0 (CC-BY).The intramolecular exchange interactions within the single-molecule magnet (SMM) "butterfly" molecule [Fe3Ln(μ3-O) 2(CCl3COO)8(H2O)(THF)3], where Ln(III) represents a lanthanide cation, are determined in a combined experimental [x-ray magnetic circular dichroism (XMCD) and vibrating sample magnetometer (VSM)] and theoretical work. Compounds with Ln=Gd and Dy, which represent extreme cases where the rare earth presents single-ion isotropic and uniaxial anisotropy, on one hand, and with Ln=Lu and Y(III) as pseudolanthanide substitutions that supply a nonmagnetic Ln reference case, on the other hand, are studied. The Dy single-ion uniaxial anisotropy is estimated from ab initio calculations. Low-temperature (T 2.5 K) hard x-ray XMCD at the Ln L 2,3 edges and VSM measurements as a function of the field indicate that the Ln moment dominates the polarization of the molecule by the applied field. Within the {Fe3LnO2} cluster the Ln-Fe3 subcluster interaction is determined to be antiferromagnetic in both Dy and Gd compounds, with values J Dy-Fe3=-0.4 K and J Gd-Fe3=-0.25 K, by fitting to spin Hamiltonian simulations that consider the competing effects of intracluster interactions and the external applied magnetic field. In the uniaxial anisotropic {Fe3DyO2} case, a field-induced reorientation of the Fe3 and Dy spins from an antiparallel to a parallel orientation takes place at a threshold field (μ0H=4 T). In contrast, in isotropic {Fe3GdO2} this reorientation does not occur. © 2013 American Physical Society.The financial support of Spanish MINECO Grant No. MAT2011-23791, the Alexander Von Humboldt Foundation (D.P.), and Aragonese DGA-IMANA E34 (cofunded by Fondo Social Europeo) and that received from European Union FEDER funds are also acknowledged. L.B.R. acknowledges the Spanish MINECO FPU 2010 grant.Peer Reviewe