Dysprosium Analogue Research Articles

Borotropic shifting of the hydrotris[3-(2-furyl)pyrazol-1-yl]borate ligand in high-coordinate lanthanide complexes

The coordination of hydrotris[3-(2-furyl)pyrazol-1-yl]borate (Tp2-Fu, C21H16BN6O3) to lanthanide(III) ions is achieved for the first time with the complex [Ln(Tp2-Fu)2](BPh4)·xCH2Cl2 (1-Ln has Ln = Ce and x = 2; 1-Dy has Ln = Dy and x = 1). This was accomplished via both hydrous (Ln = Ce) and anhydrous methods (Ln = Dy). When isolating the dysprosium analogue, the filtrate produced a second crop of crystals which were revealed to be the 1,2-borotropic-shifted product [Dy(κ4-Tp2-Fu)(κ5-Tp2-Fu*)](BPh4) (2) {Tp2-Fu* = hydrobis[3-(2-furyl)pyrazol-1-yl][5-(2-furyl)pyrazol-1-yl]borate}. We conclude that the presence of a strong Lewis acid and a sterically crowded coordination environment are contributing factors for the 1,2-borotropic shifting of scorpionate ligands in conjunction with the size of the conical angle with the scorpionate ligand.

Investigation of the correlation between the substituent effect of ligands and the catalytic activity/magnetic properties in fine-tuned rare-earth complexes

Amine-bis(benzothiazole phenol) ligands, C1NNBiBTHP-H2 and CLNNBiBTHP-H2 ligands, were designed for yttrium complexes with analogous structures. A series of nitrophenolate (NP)-type of ligands possessing R substituents with variable electronic properties (R = NO2, Cl, H, CH3) on ortho and/or para position attached to the phenolate rings have been selected as secondary ligands for complexes syntheses. Ten novel yttrium complexes have been synthesized, [Y(C1NNBiBTHP)(NP)(MeOH)] (1–5) and [Y(CLNNBiBTHP)(NP)(MeOH)] (6–10) where the secondary ligand NP = 2,4-dinitrophenol(1 and 6), 2,5-dinitrophenol (2 and 7), 2-nitrophenol (3 and 8), 4-chloro-2-nitrophenol (4 and 9) and 4-methyl-2-nitrophenol (5 and 10), as well as the structures and catalytic properties for lactide (LA) polymerization were both studied. All the core structures and coordination geometries for complexes 1–10 were isostructural. All complexes were demonstrated to be active catalysts for LA polymerization, and the catalytic performance for these complexes was compared. The dysprosium analogues (11, 12 with C1NNBiBTHP-H2 and 13, 14 with CLNNBiBTHP-H2) also been synthesized and the magnetic properties of these compounds are fully studied. Comparing a series of nitrophenolate co-ligands in two different ligand systems, we presented the first example to study the correlation between electronic effect of the ligands and catalytic properties for mononuclear rare-earth complexes.

Lanthanide dimers in coordination chains constructed by sole dicarboxylate ligand for single-molecule magnet behavior and magnetocaloric effect

The solvothermal reaction of Dy(III) and Gd(III) ions with 2,5-di‑hydroxy-benzene-1,4-di-carboxylic acid (H4dhbdc) produced two new isostructural lanthanide(III) coordination chains with the general formula {[Ln2(H2dhbdc)3(H2O)8]·6H2O}n [Ln = Dy (1) and Gd (2)]. The chains consist of carboxylate-bridged dilanthanide(III) units linked by H2dhbdc2− ligands in an end-to-end bridging mode. The Dy3+ and Gd3+ ions are located in slightly distorted biaugmented trigonal prism (C2v) and triangular dodecahedron (D2d) coordination environments, respectively. Magnetic studies reveal the extremely weak antiferromagnetic interaction (J = -0.041 cm−1) between the magnetically isotropic GdIII ions in 2. The dysprosium analogue was found to exhibit single-molecule magnet (SMM) behavior with a prominent QTM effect under zero dc field, which is largely due to large single-ion magnetic anisotropy of individual Dy3+ ions and weak antiferromagnetic interaction. For the gadolinium chain, the magnetocaloric effect (MCE) was observed with a magnetic entropy change of 20.2 J kg−1 K − 1. These results demonstrate a dicarboxylate synthetic route for the preparation of coordination polymers containing dilanthanide units for SMM and MCE applications.

Synthesis, Structures, and Luminescent Properties of Chloride and Nitrate LnIIIComplexes Coordinated by tris(Pyrazolyl)methane

AbstractWe report the synthesis of Ln3+nitrate [Ln(Tpm)(NO3)3] ⋅ MeCN (Ln=Yb (1Yb), Eu (1Eu)) and chloride [Yb(Tpm)Cl3] ⋅ 2MeCN (2Yb), [Eu(Tpm)Cl2(μ‐Cl)]2(2Eu) complexes coordinated by neutral tripodal tris(3,5‐dimethylpyrazolyl)methane (Tpm). The crystal structures of1Lnand2Lnwere established by single crystal X‐ray diffraction, while for1Ybhigh resolution experiment was performed. Nitrate complexes1Lnare isomorphous and both adopt mononuclear structure. Chloride2Ybis monomeric, while Eu3+analogue2Euadopts a binuclear structure due to two μ2‐bridging chloride ligands. The typical lanthanide luminescence was observed for europium complexes (1Euand2Eu) as well as for terbium and dysprosium analogues ([Ln(Tpm)(NO3)3] ⋅ MeCN, Ln=Tb (1Tb), Dy (1Dy); [Ln(Tpm)Cl3] ⋅ 2MeCN, Ln=Tb (2Tb), Dy (2Dy)).

Synthesis and Crystallographic Characterization of a Reduced Bimetallic Yttrium ansa-Metallocene Hydride Complex, [K(crypt)][(μ-CpAn)Y(μ-H)]2 (CpAn = Me2Si[C5H3(SiMe3)-3]2), with a 3.4 Å Yttrium-Yttrium Distance.

The reduction of a bimetallic yttrium ansa-metallocene hydride was examined to explore the possible formation of Y-Y bonds with 4d1 Y(II) ions. The precursor [CpAnY(μ-H)(THF)]2 (CpAn = Me2Si[C5H3(SiMe3)-3]2) was synthesized by hydrogenolysis of the allyl complex CpAnY(η3-C3H5)(THF), which was prepared from (C3H5)MgCl and [CpAnY(μ-Cl)]2. Treatment of [CpAnY(μ-H)(THF)]2 with excess KC8 in the presence of one equivalent of 2.2.2-cryptand (crypt) generates an intensely colored red-brown product crystallographically identified as [K(crypt)][(μ-CpAn)Y(μ-H)]2. The two rings of each CpAn ligand in the reduced anion [(μ-CpAn)Y(μ-H)]21- are attached to two yttrium centers in a "flyover" configuration. The 3.3992(6) and 3.4022(7) Å Y···Y distances between the equivalent metal centers within two crystallographically independent complexes are the shortest Y···Y distances observed to date. Ultraviolet-visible (UV-visible)/near infrared (IR) and electron paramagnetic resonance (EPR) spectroscopy support the presence of Y(II), and theoretical analysis describes the singly occupied molecular orbital (SOMO) as an Y-Y bonding orbital composed of metal 4d orbitals mixed with metallocene ligand orbitals. A dysprosium analogue, [K(18-crown-6)(THF)2][(μ-CpAn)Dy(μ-H)]2, was also synthesized, crystallographically characterized, and studied by variable temperature magnetic susceptibility. The magnetic data are best modeled with the presence of one 4f9 Dy(III) center and one 4f9(5dz2)1 Dy(II) center with no coupling between them. CASSCF calculations are consistent with magnetic measurements supporting the absence of coupling between the Dy centers.

New Family of Heptanuclear Lanthanide {Ln7} Clusters: Synthesis, Structure, and Magnetic Studies

AbstractA new family of heptanuclear lanthanide complex [Ln7(L)2(LH)4(dbm)5(OH)2(CH3OH)4]⋅xCHCl3⋅yCH3OH⋅zH2O {Ln=TbIII (1), DyIII (2) and ErIII (3) and LH3=(E)‐2‐(hydroxymethyl)‐6‐(((2‐hydroxyphenyl) imino) methyl)‐4‐methylphenol} [in 1, x=6, y=3, z=3; in 2, x=5, y=1, z=6; and in 3, x=4, z=2] has been prepared in presence of lanthanide chloride(III) salts and β‐diketonate co‐ligand dibenzoylmethane (dbm). Single crystal XRD reveals heptanuclear ensemble formed by collective action of two fully deprotonated [L]3− ligands, four double deprotonated [LH]2−, two μ3‐OH− ligands, five anionic [dbm]− β‐diketonate co‐ligands and two terminal methanol solvent molecules. This heptanuclear unit comprises of two [Dy4(μ2‐O)5(μ3‐OH)]+6 core sharing a common metal vertex Dy1 through which centre of inversion has passed for overall molecule. All the complexes have been magnetically characterized and dynamic AC magnetic studies reveals slow relaxation of magnetism present in dysprosium analogue (2).

Solvent-induced structural transformation from heptanuclear to decanuclear [Co-Ln] coordination clusters: trapping of unique counteranion and understanding of aggregation pathways.

Five new cobalt(ii/iii)-lanthanide(iii)-based coordination aggregates, [LnIII3CoII2CoIII2(L1)2(O2CCMe3)8(OH)4(OMe)2(H2O)4]·Ln(η1-O2CCMe3)2(η2-O2CCMe3)2(MeOH)2·2MeOH·2H2O (where Ln = Tb (1), Ho (3), and H2L1 = N-(2-hydroxyethyl)-salicylaldimine), TbIII3CoII3CoIII4(L1)4(O2CCMe3)9(OH)10(H2O) (4) and LnIII3CoII2CoIII5(L1)4(O2CCMe3)10(OH)10 (Ln = Dy (5), Ho (6)) have been synthesized and characterized, including structural analysis via single-crystal X-ray diffraction. The dysprosium analogue (2) of 1 and 3 was previously reported by us. The heptanuclear monocationic clusters in 1 and 3 were formed by placement of seven metal ions (4 Co and 3 Ln) in a vertex shared dicubane structure from the control of two Schiff base anions and crystallized in the presence of in situ generated and literature unknown counter anions Tb(η1-O2CCMe3)2(η2-O2CCMe3)2(MeOH)2- and Ho(η1-O2CCMe3)2(η2-O2CCMe3)2(MeOH)2-. Interesting solvent-induced cluster structure transformation was observed on dissolving the heptanuclear aggregates in MeCN for the formation of decanuclear clusters 4-6. These high nuclearity clusters consist of a vertex shared heptanuclear dicubane part and a curved trinuclear chain linking the two cubic halves. The dicubane unit differs from that of the heptanuclear precursors in the presence of CoII/III at the shared vertex as opposed to LnIII and the absence of OMe- bridges. HRMS (+ve) analysis shed light on the pathway of formation of these heptanuclear molecules, while at the same time revealing a different aggregation process for the decanuclear clusters.

A Giant Spin Molecule with Ninety-Six Parallel Unpaired Electrons

Unpaired electrons which are essential for organic radicals and magnetic materials are hardly to align parallel, especially upon the increasing of spin numbers. Here we show the antiferromagnetic interaction in the largest Cr(III)-RE (RE = rare earth) cluster {Cr10RE18} leads to 96 parallel electrons, forming a ground spins state ST of 48 for RE = Gd. This is so far the third largest ground spin state achieved in one molecule. Moreover, by using the classical Monte Calo simulation the exchange-coupling constants J_ij can be determined. Spin dynamics simulation reveals that the strong Zeeman effects of 18 Gd(III) ions stabilize the ground ferrimagnetic state and hinder the magnetization reversals of these spins. In addition, the dysprosium(III) analogue is an exchange-biasing single-molecule magnet. We believe the ferrimagnetic approach and analytical protocol established in this work can be applied generally in constructing and analysing giant spin molecules.

The differential magnetic relaxation behaviours of slightly distorted triangular dodecahedral dysprosium analogues in a type of cyano-bridged 3d-4f zig-zag chain compounds.

A class of cyano-bridged 3d-4f zig-zag chain compounds, {RE[TM(CN)6] (PNO)2(H2O)4}·(H2O) {RE = YIII, TM = [FeIII]LS (1); RE = DyIII, TM = [FeIII]LS (2), CoIII (3)}, have been synthesized and characterized by single-crystal X-ray diffraction. The rare earth ions in these compounds are situated in a slightly distorted triangular dodecahedral (D2d) coordination environment. The magnetic properties of compounds 1-3 have been comparatively studied in detail. Under a zero dc field, the temperature dependence of ac susceptibility measurements for YFe (1) indicates the absence of magnetic relaxation stemming from the single anisotropic [FeIII]LS ion. The dysprosium analogue DyFe (2) shows only magnetic relaxation behavior with a prominent QTM effect, while DyCo (3) exhibits SIM properties not completely covered by QTM, with an extracted energy barrier of 73 K under a zero dc field. The ab initio calculations indicate that both compounds 2 and 3 are SMMs with well-behaved magnetic relaxation properties primarily from the individual DyIII ion. Therefore, the different magnetic behaviors exhibited by compound 2 compared to 3 may be ascribed to the stronger QTM effect caused by the extra weak interaction of [FeIII]LS ions in 2 as a fluctuating transverse field around the DyIII ion. The QTM effect for both 2 and 3 is suppressed under an applied dc field with an effective energy barrier of 134 and 150 K, respectively. Compared with compound 2, the higher extracted Ueff/kB and χ''(T) peak temperature for 3 should be further attributed to its slightly higher single-ion axiality as calculated and the elimination of the transverse field from the [FeIII]LS ion.

Phosphoryl-Ligand Adducts of Rare Earth-TriNOx Complexes: Systematic Studies and Implications for Separations Chemistry

Phosphoryl ligands of the general formula O═PR3 (R = Me, OMe, Et, nBu, Ph, iPr, NMe2) were coordinated to [Nd(TriNOx)] (TriNOx3– = ([(2-tBuNO)C6H4CH2]3N)3–), and the resulting complexes were characterized. Solution equilibrium constants for each complex were determined, demonstrating a large range for phosphoryl ligands’ Lewis basicity. Thermogravimetric analyses provided evidence for the qualitative thermodynamic preference of phosphoryl ligands for [Nd(TriNOx)] over the dysprosium analogue. These findings were exploited for the separation of binary mixtures of neodymium/dysprosium and lanthanum/neodymium. Implementation of phosphoryl ligands in the TriNOx separation system expands its scope and demonstrates a fundamentally different mode for separating rare-earth cations based on adducts with neutral donors.

Two new POM-based compounds modified by lanthanide-Schiff base complexes with interesting NLO properties.

Two POM-based lanthanide derivatives, namely {triaqua[2,6-diacetylpyridine bis(semicarbazone)-κ5O,N,N',N'',O']terbium(III)}-μ-oxido-[tricosa-μ2-oxido-dodecaoxido-μ12-phosphato-dodecamolybdenum(VI)] pentahydrate (1), [Tb(C11H15N7O2)(H2O)3][PMo12O40]·5H2O, and the dysprosium(III) analogue (2), have been isolated successfully by the reaction of Keggin-POM [PMo12O40]3- (abbreviated as PMo12), the Ln3+ ion and the Schiff base 2,6-diacetylpyridine bis(semicarbazone) (DAPSC) ligand under hydrothermal conditions. [Ln(DAPSC)(H2O)3][PMo12O40]·5H2O is a PMo12-supported cluster featuring a lanthanide-Schiff base complex [denoted Ln-L(Schiff base)]. Single-crystal X-ray diffraction analysis reveals that the LnIII ion is in a distorted tricapped trigonal prismatic arrangement, coordinated by six O atoms and three N atoms. Two O atoms and three N atoms are provided by one DAPSC ligand, while the additional O atoms originate from a PMo12 cluster and three water molecules. Hydrogen-bonding interactions between adjacent clusters form an interesting three-dimensional supramolecular structure. The identities of 1 and 2 were characterized by IR spectroscopy, thermogravimetric analysis and powder X-ray diffraction. Interestingly, both compounds possess excellent two-photon absorption (TPA) responses to the third-order nonlinear optics (NLO) (2264 GM for 1 and 941 GM for 2), suggesting that they have potential applications in the field of nonlinear optics (NLO). To our knowledge, 1 and 2 are the first POM-based Ln-L(Schiff base) complexes showing excellent two-photon responses. Meanwhile, the electrochemical properties of both compounds were studied in detail.

Synthesis and magneto-structural studies on a new family of carbonato bridged 3d-4f complexes featuring a [CoLn(CO3)] (Ln = La, Gd, Tb, Dy and Ho) core: slow magnetic relaxation displayed by the cobalt(ii)-dysprosium(iii) analogue.

A new family of [3 + 3] hexanuclear 3d-4f complexes [(μ3-CO3){CoIILnIIIL(μ3-OH)(OH2)}3]-(ClO4)·mC2H5OH·nH2O (1-5) [Ln = La (1), Gd (2), Tb (3), Dy (4), and Ho (5)] have been prepared in moderate to high yields (62-78%) following a self-assembly reaction between the ligand 6,6',6''-(nitrilotris(methylene))tris-(2-methoxy-4-methylphenol) (H3L), Co(OAc)2·4H2O and the lanthanide ion precursors in the mandatory presence of tetrabutylammonium hydroxide. During the reaction, atmospheric carbon dioxide is fixed in the product molecule as a bridging carbonato ligand which connects all the three lanthanide centers of this molecular assembly through a rare η2:η2:η2-μ3 mode of bridging as revealed from X-ray crystallography. The metal centers in all these compounds, except the GdIII analogue (2), are coupled in antiferromagnetic manner while the nature of coupling in the CoGd complex is ferromagnetic. DFT calculations revealed that this ferromagnetic interaction occurs most likely by the CoII-GdIII superexchange, mediated via the bridging oxygen atoms. Only the CoII-DyIII compound (4) displayed a slow relaxation of the magnetization at a very low temperature as established by AC susceptibility measurements. The data provides an estimation of the activation energy U/kB = 9.2 K and the relaxation time constant τ0 = 1.0 × 10-7 s.

Exchange-coupled terbium-radical complex Tb-phNO showing slow reversal of magnetization

A novel terbium(III)-nitroxide complex [TbIII(hfac)3(phNO)(H2O)] (phNO=tert-butyl phenyl nitroxide, hfac=1,1,1,5,5,5-hexafluoropentane-2,4-dionate) was synthesized towards development of 4f-2p compounds with strong ferromagnetic exchange coupling. There are two crystallographically independent molecules in a unit cell. The ac magnetic susceptibility at Hdc=2000Oe showed double χm″ peaks accompanied by frequency dependence and afforded Ueff(1)/kB=46.3(7)K with τ0(1)=1.9(3)×10−9s for the high-temperature peak series and Ueff(2)/kB=21(2)K with τ0(2)=1.3(9)×10−8s for the low-temperature peak series. Every molecule is proven to behave as a potential single-molecule magnet (SMM). In contrast, the corresponding dysprosium(III) analogue did not exhibit meaningful out-of-phase ac magnetic susceptibility. In the strongly exchange-coupled regime owing to the direct radical coordination bond, the whole molecular electron counting may provide a useful criterion to predict Kramers molecules as potential SMM candidates.

Heterometallic trinuclear {CoLn(III)} (Ln = Gd, Tb, Ho and Er) complexes in a bent geometry. Field-induced single-ion magnetic behavior of the Er(III) and Tb(III) analogues.

Through the use of a multi-site compartmental ligand, 2-methoxy-6-[{2-(2-hydroxyethylamino)ethylimino}methyl]phenol (LH3), the family of heterometallic, trinuclear complexes of the formula [CoLn(L)2(μ-O2CCH3)2(H2O)3]·NO3·xMeOH·yH2O has been expanded beyond Ln = Dy(III) to include Gd(III) (), Tb(III) (), Ho(III) () and Er(III) () for , and (x = 1; y = 1) and for (x = 0; y = 2). The metallic core of these complexes consists of a (Co(III)-Ln(III)-Co(III)) motif bridged in a bent geometry resulting in six-coordinated distorted Co(III) octahedra and nine-coordinated Ln(III) monocapped square-antiprisms. The magnetic characterization of these compounds reveals the erbium and terbium analogues to display a field induced single-ion magnetic behavior similar to the dysprosium analogue but at lower temperatures. The energy barrier for the reversal of the magnetization of the CoTb(III) analogue is Ueff ≥ 15.6(4) K, while for the CoEr(III) analogue Ueff ≥ 9.9(8) K. The magnetic properties are discussed in terms of distortions of the 4f electron cloud.

Thiacalix[4]arene-supported heterodinuclear NiII–LnIII complexes: slow magnetic relaxation behavior in the dysprosium analogue

Three thiacalix[4]arene-supported ferromagnetic NiII–LnIII complexes have been isolated. The dysprosium analogue exhibits field-induced SMM behavior and diamagnetic dilution can efficiently influence the dipole–dipole interaction between magnetic centers.

Nanoscale {LnIII(24)ZnII(6)} Triangular Metalloring with Magnetic Refrigerant, Slow Magnetic Relaxation, and Fluorescent Properties.

The self-assembly of Ln(ClO4)3 · 6H2O and Zn(OAc)2 · 2H2O with pyrazine-2-carboxylic acid (HL) results in the formation of three novel nanosized {LnIII(24)ZnII(6)} triangular metallorings, [Gd24Zn6L24(OAc)22(μ3-OH)30(H2O)14](ClO4)7(OAc) · 2CH3OH · 26H2O (1), [Tb24Zn6L24(OAc)22(μ3-OH)30(CH3O)2(CH3OH)2(H2O)10](ClO4)5(OH) · 6CH3OH · 12H2O (2), and (H3O)[Dy24Zn6L24(OAc)22(μ3-OH)30(H2O)14](ClO4)7(OAc)2 · 4CH3OH · 22H2O (3), having the largest nuclearity among any known Ln/Zn clusters. Magnetic and luminescent studies reveal the special prowess for each lanthanide complex. Magnetic studies reveal that 1 exhibits a significant cryogenic magnetocaloric effect with a maximum -ΔSm (isothermal magnetic entropy change) value of 30.0 J kg(-1) K(-1) at 2.5 K and 7 T and that a slow magnetization relaxation is observed for the dysprosium analogue. In addition, the solid-state photophysical properties of 2 display strong characteristic Tb(III) photoluminescent emission in the visible region, suggesting that Tb(III)-based luminescence is sensitized by the effective energy transfer from the ligand HL to the metal centers.

Synthesis, structures and magnetism of heterodinuclear Ni–Ln complexes: field-induced single-molecule magnet behavior in the dysprosium analogue

Three isomorphous Ni–Ln heterodinuclear complexes were synthesized and structurally characterized. The Dy derivative exhibits field-induced single-molecule magnet behavior with an effective energy barrier of 16.9 K under a 1000 Oe dc field.

Lanthanide nonanuclear clusters with sandglass-like topology and the SMM behavior of dysprosium analogue

The reaction of a polyhydroxy Schiff-base of 2-(((2-hydroxy-3-methoxyphenyl)methylene)amino)-2-(hydroxymethyl)-1,3-propanediol (H4L) with lanthanide(III) nitrate salts in the presence of triethylamine as the base afforded five nonanuclear lanthanide clusters with sandglass-like topology, namely, [Ln9L4(μ4-OH)2(μ3-OH)8(NO3)8(CH3OH)2 (H2O)2](NO3)·xMeOH·yH2O·zCH2Cl2 (Ln=Tb (1, x=7), Dy (2, x=4, y=9), Ho (3, x=4, y=6), Er (4, x=7), Yb (5, x=4, z=3)). They were characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy and magnetic susceptibility. The magnetic studies of 1–5 revealed the presence of dominant antiferromagnetic interactions between their metal centers. The DyIII analogue shows single-molecule magnetism behavior.

Dinuclear Lanthanide–Carboxylate Compounds: Field-Induced Slow Relaxation of Magnetization for Dysprosium(III) Analogue

Three chiral dinuclear lanthanide compounds, Ln2(µ2-L)4(L)2(phen)2 (Ln = Dy (1), Gd (2), and Er (3); phen = 1,10-phenanthroline), have been synthesized using the (S)-(+)-2-(6-methoxy-2-naphthyl)propionic acid (HL) ligand. The two lanthanide centres in compound Ln2(µ2-L)4(L)2(phen)2 are bridged by four carboxylate groups to give a dinuclear Ln2(µ2-L)4 core. The square antiprismatic coordination environment for each lanthanide centre is further completed by a chelating carboxylate group from another L– ligand and two nitrogen atoms from the phen ligand. A weak antiferromagnetic interaction between the two GdIII ions is observed in compound 2. The Dy analogue displays field-induced slow magnetic relaxation behaviour with an effective energy barrier Ueff/k of 17.24(2) K and a pre-exponential factor τ0 of 2.7(1) × 10–6 s. However, no slow relaxation phenomenon was observed for the Er derivative even in the presence of 2 kOe applied field.

Synthesis, crystal structure and study of magnetocaloric effect and single molecular magnetic behaviour in discrete lanthanide complexes.

The synthesis, crystal structure and magnetic properties of four polynuclear lanthanide coordination complexes having molecular formulae, [Gd3(2)(1)L(H2O)8(Cl)](Cl)4·10H2O (1), [Dy3L(2)(1)(H2O)9](Cl)5·6H2O (2) [Gd6L(2)(2)(HCO2)4(μ3-OH)4(DMF)6(H2O)2](Cl)2·4H2O (3) and [Dy6L(2)(2)(HCO2)4(μ3-OH)4(DMF)6(H2O)2](Cl)2·4H2O (4) (where H2L(1) = bis[(2-pyridyl)methylene]pyridine-2,6-dicarbohydrazide and H4L(2) = bis[2-hydroxy-benzylidene]pyridine-2,6-dicarbohydrazide) are reported. Structural investigation by X-ray crystallography reveals similar structural features for complexes 1 and 2 and they exhibit butterfly like shapes of the molecules. Non-covalent interactions between the molecules create double helical arrangements for both molecules. Complexes 3 and 4 are isostructural and the core structures feature four distorted hemi-cubanes connected by vertex sharing. Magnetic studies unveil significant magnetic entropy changes for complexes 1, 3 and slow relaxation of magnetization for both dysprosium analogues 2 and 4.