Magdalena Fitta

Magnetocaloric effect in M–pyrazole–[Nb(CN)8] (M = Ni, Mn) molecular compounds

We report a study of magnetocaloric effect (MCE) in cyanido-bridged {[M(II)(pyrazole)(4)](2)[Nb(IV)(CN)(8)]·4H(2)O}(n) molecular compounds where M = Ni, Mn, pyrazole = C(3)H(4)N(2). The substances show a sharp phase transition to a long range magnetically ordered state, with ferromagnetic coupling between M and Nb sublattices in the case of the Ni-based sample 1 (T(c) = 13.4 K) and ferrimagnetic coupling for the Mn-based sample 2 (T(c) = 23.8 K). The magnetic entropy change ΔS due to applied field change ΔH as a function of temperature was determined by the magnetization and heat capacity measurements. The maximum value of ΔS at μ(0)ΔH = 5 T is 6.1 J mol(-1) K(-1) (5.9 J kg(-1) K(-1)) for 1 at T = 14 K and 6.7 J mol(-1) K(-1) (6.5 J kg(-1) K(-1)) for 2 at T = 25 K. MCE data at different applied fields have been presented as one universal curve, which confirms magnetic transitions in 1 and 2 to be of second order. The temperature dependences of the n exponent characterizing the dependence of ΔS on ΔH have been obtained. The n(T(c)) values, consistent with the shape of the magnetization curves, pointed to the 3D Heisenberg behaviour for 2 and some anisotropy, probably of the XY type, for 1. The (H/T(c))(2/3) dependence of the maximum entropy change has been tested in the ferrimagnetic Mn(2)-L-[Nb(CN)(8)] (L = C(3)H(4)N(2), C(4)H(4)N(2)) series.

Magnetocaloric effect and critical behaviour in Mn2–pyridazine–[Nb(CN)8] molecular compound under pressure

A comprehensive study of magnetocaloric effect (MCE) and critical behaviour in the ferrimagnetic Mn2–pyridazine–[Nb(CN)8] molecular magnet under hydrostatic pressure is reported. The pressure-induced structural changes provoke the strengthening of magnetic interaction between Mn and Nb centres. Consequently, an increase of critical temperature Tc is observed from 43 K for a sample at ambient pressure (A) to 52.5 K for a sample under a pressure of 1.19 GPa (AHP). The magnetocaloric effect was determined by the magnetization measurements. The application of a hydrostatic pressure of 1.19 GPa causes a decrease in the maximum value of magnetic entropy change ΔS, which for AHP is equal to 4.63 J mol−1 K−1 (7.73 J kg−1 K−1) at μ0ΔH = 5 T, while for A it is 5.36 J mol−1 K−1 (8.95 J kg−1 K−1) for the same magnetic field change. The temperature-dependent parameter n obtained for AHP, describing the field dependence of MCE, is consistent with other critical exponents determined from magnetization measurements. The critical exponents allow us to classify AHP to the 3D Heisenberg universality class, similar to the case of the non-pressurized sample.

A Family of Octahedral Magnetic Molecules Based on [NbIV(CN)8]4–

A building block approach has been used to prepare a new family of hexanuclear magnetic molecules Mn4Nb2, Fe4Nb2, and Co4Nb2 of general formula {[MII(tmphen)2]4[NbIV(CN)8]2}·solv (M = Mn, Fe, Co; tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline; solv = MeOH and/or H2O). Mn4Nb2 exhibits a magnetocaloric effect at temperatures close to 1.8 K, and Fe4Nb2 undergoes an incomplete gradual spin crossover and a photomagnetic response related to light-induced excited spin state trapping.

Heat capacity, magnetic and lattice dynamic properties of TbMn1-xFexO3

The effect of substitution of Fe3+ ions by Mn3+ ions on crystal structure, lattice dynamic, heat capacity and magnetic properties in TbMn1-xFexO3 ceramics has been studied. X-ray powder diffraction and Raman spectroscopy revealed that lattice distortion can be mainly attributed to Jahn-Teller distortion and tilting of octahedrons for samples with x < 0.4; for higher Fe concentration, the distortions are dominated by the octahedra tilting with less contribution of the Jahn-Teller effect. The anomalies in heat capacity of parent compounds (TbMnO3 and TbFeO3), which are associated with magnetic transitions, are smeared out by ion substitution. Magnetization measurements indicate that magnetic ordering persists in whole concentration range. The butterfly-type magnetic hysteresis loops suggest that the magnetic ground state of the whole system is complex and thence interesting for next experimental and theoretical studies.

MOKE magnetometry as a probe of surface magnetic impurities in electropolymerized magnetic thin films of the Prussian blue analogue Fe3[Cr(CN)6]2·15 H2O

A magneto-optical Kerr effect (MOKE) study has been performed on electrodeposited thin films of the Prussian blue analogue Fe3[Cr(CN)6]2·15H2O (1). This study reveals the onset of hysteretic magnetic signals at temperatures above 60 K, in contrast with magnetic susceptibility measurements which indicate a Curie temperature of 23 K for this ferromagnetic film. The origin of this discrepancy is due to the presence of amorphous iron oxide particles that accumulate in the surface of the material. This report illustrates the potential of MOKE magnetometry for the detection of surface chemical impurities that remain elusive using bulk magnetic techniques.

Magnetic and magneto-optical properties of nickel hexacyanoferrate/chromate thin films

One of the most important challenges of modern science and technology is the quest for novel and tuneable materials, the properties of which can be widely controlled by chemical modifications or external stimuli. Simultaneously, an interest in the development of magnetic thin films also gains significant attention. In the current paper we bring together both these challenges and present a study of a new type of low-dimensional nickel hexacyanoferrate/chromate system. Thin films were obtained by the “layer by layer” deposition technique, where the ratio of Fe/Cr was controlled by the dipping sequence. The scope of this work is a comprehensive analysis of structural, spectroscopic and magnetic properties of the compound and the investigation of the evolution of material properties induced by the change of the chemical composition.

Crystalline bilayers unzipped and rezipped: solid-state reaction cycle of a metal–organic framework with triple rearrangement of intralayer bonds

We present a series of remarkable structural transformations for a family of layered metal–organic frameworks (MOFs) in a three-step solid-state reaction cycle. The cycle represents new dynamic behavior of 2D coordination polymers and involves the sequence of reactions: {[Mn2(ina)4(H2O)2]·2EtOH}n (JUK-1) → {(NH4)2[Mn(ina)2(NCS)2]}n·xH2O (JUK-2) → {[Mn2(ina)2(Hina)2(NCS)2]}n (JUK-3) → JUK-1 (Hina = isonicotinic acid), each accompanied by rearrangement of intralayer coordination bonds and each induced by a different external stimulus. In situ investigation of the first step of the cycle by combined synchrotron X-ray diffraction and Raman spectroscopy reveals direct mechanochemical unzipping of JUK-1 bilayers to respective JUK-2 layers with reaction rates dependent on the milling conditions. In contrast, the reverse zipping of JUK-2 layers involves two steps and proceeds through a new MOF (JUK-3) whose structure was elucidated by powder X-ray diffraction. Magnetic measurements confirm conversions of manganese nodes in the reaction cycle. The findings indicate the possibility of developing coordination-based assemblies with large structural responses for use in smart stimuli-responsive systems and sensor technologies.

Relaxation and magnetocaloric effect in the Mn12 molecular nanomagnet incorporated into mesoporous silica: a comparative study

This paper presents the synthesis and investigation of the magnetic properties of mesoporous silica SBA-15 functionalized with Mn12 ([Mn12O12(CH3COO)16(H2O)4]·2CH3COOH·4H2O) high-spin molecular clusters. The SBA-Mn12 sample has been examined by means of X-ray diffraction, infrared spectroscopy, nitrogen sorption and TEM techniques. AC and DC magnetic measurements, including measurements of the magnetocaloric effect (MCE) were carried out both for SBA-Mn12 and for polycrystalline Mn12. An increase in the activation energy and in the distribution of relaxation times was observed for SBA-Mn12 as compared to those of Mn12. Differences in the MCE were also revealed. The maximum magnetic entropy change at the field change of 50 kOe for SBA-Mn12 is equal to 13.8 J K−1 mol−1 at T = 2.8 K, which is significantly less than 25.3 J K−1 mol−1 observed for Mn12 at 3.2 K. The altered relaxation and the magnetocaloric effect point to a successful incorporation of Mn12 molecules into the silica channels.

Magnetic Systems at Criticality: Different Signatures of Scaling

Different aspects of critical behaviour of magnetic materials are presented and discussed. The scaling ideas are shown to arise in the context of purely magnetic properties as well as in that of thermal properties as demonstrated by magnetocaloric effect or combined scaling of excess entropy and order parameter. Two non-standard approaches to scaling phenomena are described. The presented concepts are exemplified by experimental data gathered on four representatives of molecular magnets.

Dinuclear molecular magnets with unblocked magnetic connectivity: magnetocaloric effect

A detailed study of the magnetocaloric effect in two isostructural bimetallic compounds {[MII(H2O)2]2[NbIV(CN)8]·4H2O}n (M = Mn, Fe) is presented. The substances show sharp phase transitions to the long-range magnetically ordered state with ferromagnetic coupling between M and Nb sublattices in the case of the Fe-based sample (FeNb, Tc = 43 K) and antiferromagnetic coupling for the Mn-based sample (MnNb, Tc = 50 K). The magnetic entropy change was found to reach 5.07 J mol−1 K−1 (9.09 J kg−1 K−1) for MnNb and 4.82 J mol−1 K−1 (8.65 J kg−1 K−1) for FeNb under the applied magnetic field change of 5 T. Isothermal entropy changes corresponding to different field changes are demonstrated to collapse on a single master curve, which confirms the magnetic transitions in FeNb and MnNb to be of the second order. The results obtained for FeNb and MnNb are discussed in the context of MCE tunability by un/blocking of magnetic connectivity through dis/reconnection of spatially extended ligands.