First heterometallic GaIII-DyIII single-molecule magnets: Implication of GaIII in extracting Fe-Dy interaction

The compounds of the system [M4M′2(μ3-OH)2(nbdea)4(C6H5CO2)8]·MeCN, where M = GaIII, M′ = DyIII (2), M = FeIII, M′ = YIII (3) are isostructural to the known [Fe4Dy2] compound (1). Those of the system [M4M′4(μ3-OH)4(nbdea)4(m-CH3C6H4CO2)12]·nMeCN, where M = GaIII, M′ = DyIII, n = 4 (5), M = FeIII, M′ = YIII, n = 1 (6) are isostructural to the [Fe4Dy4] compound (4). This allows for comparisons between single ion effects of the paramagnetic ions. The structures were determined using single crystal analysis. Magnetic susceptibility measurements reveal that the GaIII–DyIII compounds 2 and 5 are SMMs. The energy barrier for 2 is close to that for the known isostructural Fe4Dy2 compound (1), but with a significantly increased relaxation time

Mechanism of magnetisation relaxation in M III 2 Dy III 2 (M = Cr, Mn, Fe, Al) “butterfly” complexes: How important are the transition metal ions here?

We describe the synthesis, characterisation and magnetic studies of four tetranuclear, isostructural “butterfly” heterometallic complexes: [MIII 2 LnIII 2 (m3-OH)2(p-Me-PhCO2)6(L)2] (H2 L ¼ 2,20-((pyridin-2-ylmethyl)azanediyl)bis(ethan-1-ol), M ¼ Cr, Ln ¼ Dy (1), Y (2), M ¼ Mn, Ln ¼ Dy (3), Y (4)), which extend our previous study on the analogous 5 {Fe2Dy2}, 6 {Fe2Y2} and 7 {Al2Dy2} compounds. We also present data on the yttrium diluted 7 {Al2Dy2}: 8 {Al2Dy0.18Y1.82}. Compounds dc and ac magnetic susceptibility data reveal single-molecule magnet (SMM) behaviour for complex 3 {Mn2Dy2}, in the absence of an external magnetic field, with an anisotropy barrier Ueff of 19.2 K, while complex 1 {Cr2Dy2}, shows no ac signals even under applied dc field, indicating absence of SMM behaviour. The diluted sample 8 {Al2Dy0.18Y1.82} shows field induced SMM behaviour with an anisotropy barrier Ueff of 69.3 K. Furthermore, the theoretical magnetic properties of [MIII 2 LnIII 2 (m3-OH)2(p-Me-PhCO2)6(L)2] (M ¼ Cr, 1 or Mn, 3) and their isostructural complexes: [MIII 2 DyIII 2 (m3-OH)2(p-Me-PhCO2)6(L)2] (M ¼ Fe, 5 or Al, 7) are discussed and compared. To understand the experimental observations for this family, DFT and ab initio CASSCF + RASSI-SO calculations were performed. The experimental and theoretical calculations suggest that altering the 3dIII ions can affect the single-ion properties and the nature and the magnitude of the 3dIII–3dIII, 3dIII–DyIII and DyIII–DyIII magnetic coupling, thus quenching the quantum tunneling of magnetisation (QTM) significantly, thereby improving the SMM properties within this motif. This is the first systematic study looking at variation and therefore role of trivalent transition metal ions, as well as the diamgnetic AlIII ion, on slow relaxation of magnetisation within a series of isostructural 3d–4f butterfly compounds

Assisted Self-Assembly to Target Heterometallic Mn-Nd and Mn-Sm SMMs: Synthesis and Magnetic Characterisation of [Mn7_{7}Ln3_{3}(O)4_{4}(OH)4_{4}(mdea)3_{3}(piv)9_{9}(NO3_{3})3_{3}] (Ln=Nd, Sm, Eu, Gd)**

Assisted self-assembly by using a preformed [Mn$_{6}$O$_{2}$(piv)$_{10}$(4-Me-py)$_{2}$(pivH)$_{2}$] (1) (pivH=pivalic acid) cluster leads to 3 different outcomes of the reaction with Ln(NO$_{3}$)$_{3}$ ⋅ xH$_{2}$O (Ln=Pr−Ho and Y): Mn$_{7}$Ln$_{3}$ and in some cases the inverse butterfly Mn$_{2}$Ln$_{2}$ for Ln=Pr−Eu, Mn$_{5}$Ln$_{4}$ for Ln=Tb-Ho and in the special case of Gd all three possibilities can form. Whilst the magnetic properties for the Mn$_{5}$Ln$_{4}$ systems show the expected known SMM properties, for Mn$_{7}$Ln$_{3}$ two new examples of Nd- and Sm-containing SMMs have been discovered. in an assisted self-assembly approach starting from the [Mn$_{6}$O$_{2}$(piv)$_{10}$(4-Me-py)$_{2}$(pivH)$_{2}$] cluster a family of Mn−Ln compounds (Ln=Pr−Yb) was synthesised. The reaction of [Mn$_{6}$O$_{2}$(piv)$_{10}$(4-Me-py)$_{2}$(pivH)$_{2}$] (1) with N-methyldiethanolamine (mdeaH$_{2}$) and Ln(NO$_{3}$)$_{3}$ ⋅ 6H$_{2}$O in MeCN generally yields two main structure types: for Ln=Tb−Yb a previously reported Mn$_{5}$Ln$_{4}$ motif is obtained, whereas for Ln=Pr−Eu a series of Mn$_{7}$Ln$_{3}$ clusters is obtained. Within this series the Gd$^{III}$ analogue represents a special case because it shows both structural types as well as a third Mn$_{2}$Ln$_{2}$ inverse butterfly motif. Variation in reaction conditions allows access to different structure types across the whole series. This prompts further studies into the reaction mechanism of this cluster assisted self-assembly approach. For the Mn$_{7}$Ln$_{3}$ analogues reported here variable-temperature magnetic susceptibility measurements suggest that antiferromagnetic interactions between the spin carriers are dominant. Compounds incorporating Ln=Nd$^{III}$(2), Sm$^{III}$(3) and Gd$^{III}$ (5) display SMM behaviour. The slow relaxation of the magnetisation for these compounds was confirmed by ac measurements above 1.8 K

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.The projects MINECO (MAT2011/23791, MAT2011/27233-C02-02, and MAT2014/53921-R), DGA IMANA E34, and Alexander Von Humboldt Foundation (D.P.) are acknowledged for financial support.Peer Reviewe

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

Synthesis of Bimetallic Uranium and Neptunium Complexes of a Binucleating Macrocycle and Determination of the Solid-State Structure by Magnetic Analysis

Syntheses of the bimetallic uranium(III) and neptunium(III) complexes [(UI)2(L)], [(NpI)2(L)], and [{U(BH4)}2(L)] of the Schiff-base pyrrole macrocycles L are described. In the absence of single-crystal structural data, fitting of the variable-temperature solid-state magnetic data allows the prediction of polymeric structures for these compounds in the solid state.JRC.E.6-Actinides researc

One-pot synthesis of an unusual manganese-lanthanide-ferrocene cluster: A combination of d-, f-metals and an organometallic fragment

Reaction of the preformed cluster [Mn6O2(Piv) 10(4-Me-py)2.5(PivH)1.5] with Nd(NO 3)3.6H2O, N-butyldiethanolamine (bdeaH 2) and ferrocene-1,1'-dicarboxylic acid (fcdcH2) resulted in the formation of the first 3d-4f complex incorporating organometallic ferrocene [Mn4Nd4(OH)4(fcdc) 2(Piv)8(bdea)4].H2O; we report the X-ray structure and preliminary magnetic studies of this high-nuclearity cluster. © 2009 Elsevier Ltd. All rights reserved.This work was supported by the MAGMANet (NMP3-CT-2005- 515767), CFN (DFG), Contract 235 with CNCSIS and Program ‘‘Idei”.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

Synthesis and Spectroscopic Characterisation of a Heterodinuclear Iron(III)-Copper(II) Complex Based on an Asymmetric Dinucleating Ligand System

The site-directed generation of a heterodinuclear Fe IIICu II complex by using a new asymmetric dinucleating ligand FloH is reported. The iron(III) ion is introduced first on the preferential metal-binding site of the ligand that leads to the formation of the thermodynamically favored five-membered chelate rings upon metal-binding. Copper(II) is introduced in the next step. The stepwise metalation strategy reported here may be extended to the preparation of other heterometallic complexes with the view of avoiding a statistical distribution. Such complexes can offer novel spectroscopic properties, electronic structures, and reactivities in comparison to their homometallic analogues