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Dysprosium(III)??? Dysprosium(III) Interactions in a Single-Molecule Magnet

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Dysprosium(III)??? Dysprosium(III) Interactions in a Single-Molecule Magnet ARTICLE Received 11 Jul 2014 | Accepted 12 Sep 2014 | Published 13 Oct 2014 DOI: 10.1038/ncomms6243 Direct measurement of dysprosium(III)??? dysprosium(III) interactions in a single-molecule magnet Eufemio Moreno Pineda1, Nicholas F. Chilton1, Raphael Marx2, Marı´aDo¨rfel2, Daniel O. Sells1, Petr Neugebauer2, Shang-Da Jiang3, David Collison1, Joris van Slageren2, Eric J.L. McInnes1 & Richard E.P. Winpenny1 Lanthanide compounds show much higher energy barriers to magnetic relaxation than 3d-block compounds, and this has led to speculation that they could be used in molecular spintronic devices. Prototype molecular spin valves and molecular transistors have been reported, with remarkable experiments showing the influence of nuclear hyperfine coupling on transport properties. Modelling magnetic data measured on lanthanides is always com- plicated due to the strong spin–orbit coupling and subtle crystal field effects observed for the 4f-ions; this problem becomes still more challenging when interactions between lanthanide ions are also important. Such interactions have been shown to hinder and enhance magnetic relaxation in different examples, hence understanding their nature is vital. Here we are able to measure directly the interaction between two dysprosium(III) ions through multi-frequency electron paramagnetic resonance spectroscopy and other techniques, and explain how this influences the dynamic magnetic behaviour of the system. 1 School of Chemistry and Photon Science Institute, The University of Manchester, Oxford Road, Manchester M13 9PL, UK. 2 Institut fu¨r Physikalische Chemie, Universita¨t Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany. 3 1. Physikalisches Institut, Universita¨t Stuttgart, Pfaffenwaldring 57, 70569 Stuttgart, Germany. Correspondence and requests for materials should be addressed to E.J.L.M. (email: [email protected]) or to R.E.P.W. (email: [email protected]). NATURE COMMUNICATIONS | 5:5243 | DOI: 10.1038/ncomms6243 | www.nature.com/naturecommunications 1 & 2014 Macmillan Publishers Limited. All rights reserved. ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms6243 ascinating physics has been observed in lanthanide-based molecules ranging from single nuclear spin detection gz = 20 Fand manipulation1,2, blocking of magnetization at unprecedentedly high temperatures for a molecule3,4, magnetic memory in chiral systems with a non-magnetic ground state5,6 and energy barriers for loss of magnetization, U , an order of eff Dy(1) 44° magnitude higher than observed for polymetallic d-block cages7,8. A diverse range of applications has been envisioned for lanthanide (Ln) containing molecules, including use as qubits J ⊥ for quantum information processing9,10 and prototype devices Dy(1) 11 1 z such as molecular spin valves and transistors have been x y g = 13.9 reported. These advances have been very rapid since the initial z′ Dy(2) report that a terbium phthalocyanine compound could function J || as a single-molecule magnet (SMM)12. The SMM behaviour observed for Ln complexes is due to the Dy(2) large magnetic anisotropy of the individual ions, caused by strong spin–orbit coupling and the crystal field (CF) effects due to the Figure 1 | Structural analysis. (a) Crystal structure of 3. Scheme: Dy, blue; ligand environment13,14. Other interactions, for example N, light blue; O, red; C, grey; H, dark grey. Orientation of the principal intermolecular effects, often favour efficient quantum tunnelling magnetic axes for Dy(1) and Dy(2) in the ground Kramers doublet from ab of magnetization at zero external field, and this factor can mean initio calculations shown as orange arrows and that for Dy(1) from little magnetic hysteresis is seen even in compounds with very electrostatic calculations as green arrow. (b) Schematic of the magnetic 13 large Ueff . When considering polymetallic Ln complexes, the model for the EPR simulation. Relative projection of the principal magnetic situation becomes even more complicated. Radical bridging axes for Dy(1) and Dy(2), along which gz ¼ 20 and 13.9 for Dy(1) and ligands can provide a strong magnetic exchange pathway Dy(2), respectively, and the anisotropic exchange interaction between the between two lanthanide ions, leading to magnetic hysteresis at dysprosium pair. 14 K3,4. In other compounds weak Ln ÁÁÁLn interactions can shift the zero-field quantum tunnelling step to a finite field, ions, three nitrate anions and four 8-quinolinolate ligands, crys- 15 known as exchange biasing , with different effects on cryogenic tallizing with a protonated 8-hydroxyquinolinium counter-cation 16,17 magnetization curves depending on the sign of the exchange and a molecule of MeOH. Dy(1) is bound by three bridging 18 or even mask single-ion slow relaxation modes . More 8-quinolinolate ligands and a single chelating 8-quinolinolate frequently, however, Ln ÁÁÁLn interactions increase quantum ligand, generating an N4O4 coordination environment with a tunnelling rates, leading to apparently lower Ueff values when bicapped trigonal prism geometry, subsequently referred to as the compared with paramagnetic Ln ions doped into a diamagnetic ‘hq pocket’ (Fig. 1a). The Dy(2) site binds to three chelating 8,17,19 lattice . Understanding how Ln ÁÁÁLn interactions can have nitrate anions and the O-atoms from three bridging quinolinate such different and seemingly contradictory influences is ligands, yielding a highly distorted O9 environment subsequently important for improving the performance of Ln SMMs. referred to as the ‘NO3 pocket’. The eight-coordinate hq pocket is Understanding such interactions in polymetallic molecular Ln significantly smaller than the nine-coordinate NO3 pocket: the complexes is far from trivial. Part of this problem is that bulk volumes defined by the donor atoms are 130 and 140 Å3, magnetic measurements provide only indirect evidence of weak respectively. Ln ÁÁÁLn interactions which can be difficult to distinguish from As the two coordination sites are different in compounds 1–7, other contributions to the low energy physics, for example, CF we can take advantage of the lanthanide contraction to dope effects, intermolecular interactions, impurities. In this work we paramagnetic ions into one or the other of the two pockets of study a {Dy2} complex where we can spectroscopically measure a the diamagnetic yttrium or lutetium compound, 1 and 7 Dy(III) ÁÁÁDy(III) interaction that quenches SMM behaviour. respectively20. Crystallographic studies on 1:1 heterobimetallic We combine magnetic measurements, electron paramagnetic Ln-Y compounds (see Methods, Supplementary Tables 6–8 and resonance (EPR) spectroscopy, ab initio calculations and far- Supplementary Data 8–13) show that LuIII occupies the smaller infrared (FIR) spectroscopy to develop a simple model to describe hq pocket in Lu-Y, while for the Dy-Y compound there is a the magnetic interaction in a Dy ÁÁÁDy pair, and provide design distribution between the two pockets as YIII and DyIII have criteria for when this interaction will lead to exchange biasing, similar ionic radii. Therefore for DyIII doped at a low level into 7, III III and when it will lead to collapse of the SMM behaviour. hereafter {Dy@Lu2}, Dy is in the NO3 pocket, while for Dy III doped at a low level into 1, hereafter {Dy@Y2}, Dy is distributed evenly between the two pockets. Results Synthesis and structure. Hydrated lanthanide nitrate Ln(NO3)3 Á nH2O and 8-hydroxyquinoline (hqH) were combined Magnetic measurements. The room temperature wMT value for 3 in a 1:2.5 mole ratio and heated to reflux in MeOH for 3 h. Slow (26.8 cm3 K mol À 1) is close to the expected value for two non- evaporation of this solution gave yellow block-shaped X-ray interacting DyIII ions and declines smoothly on cooling reaching quality single crystals in a yield of 52–75%. Characterization by a minimum at 5 K (Fig. 2a) due to the depopulation of the CF single crystal X-ray diffraction revealed an asymmetric lanthanide states. Below 5 K wMT increases due to a weak ferromagnetic III dimer with formula [hqH2][Ln2(hq)4(NO3)3] Á MeOH (Ln ¼ Y , interaction between the paramagnetic centres. The low 1;TbIII, 2;DyIII, 3;HoIII, 4;ErIII, 5;YbIII, 6 and LuIII, 7; see temperature magnetization versus applied magnetic field does not Methods, Supplementary Tables 1 and 2 and Supplementary saturate at 1.8 K in a field of 7 T, indicating strong magnetic Data 1–7). Compounds 1–7 are isostructural, crystallizing in the anisotropy (Fig. 2a inset). monoclinic space group P21/c (Fig. 1a; see Methods and The dynamic magnetic behaviour of 3 was investigated Supplementary Tables 3–5). We focus on 3 as it has the most through alternating current (AC) magnetic susceptibility interesting magnetic properties. The dimer consists of two Dy(III) measurements, performed both with a zero and a 1 kG applied 2 NATURE COMMUNICATIONS | 5:5243 | DOI: 10.1038/ncomms6243 | www.nature.com/naturecommunications & 2014 Macmillan Publishers Limited. All rights reserved. NATURE COMMUNICATIONS | DOI: 10.1038/ncomms6243 ARTICLE 0.8 1 Hz 28 –1 0.7 10 Hz 70 Hz –3 200 Hz ) 26 12 0.6 451 Hz τ –5 K 700 Hz ln( –1 –1 B U = 41 cm –1 10 μ 0.5 957 Hz –7 eff –6 A = 1.4 ×10 s 24 1,202 Hz 0 8 mol 0.03 > > 0.55 mol 3 –9 3 0.4 6 0.1 0.2 0.3 22 / cm 1.8 K 4 M 0.3 –1 T / cm Temperature / K χ″ M 3 K χ 2 4 K 0.2 20 Magnetization / N 0 01234567 0.1 18 Field / T 0.0 0 50 100 150 200 250 300 2 4 6 8 101214161820 Temperature / K Temperature / K 0.7 1.10 3.5 K 0T/6T 1T/6T 0.6 1.05 2T/6T 3T/6T 0.5 4T/6T –1 1.00 5T/6T Experiment mol 0.4 3 12 K 0.95 0.3 / cm M 0.90 χ″ 0.2 Normalized transmission Calculation 0.1 0.85 0.0 0.80 0.5 1.0 1.5 2.0 2.5 3.0 3.5 10 20 30 40 50 60 70 80 90 χ′ 3 –1 –1 M / cm mol Energy / cm 00 Figure 2 | Magnetic measurements.
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