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    Electronic Supplementary Information

    Direct observation of a ferri-to-ferromagnetic transition

    in a fluoride-bridged 3d-4f molecular cluster

    Jan Dreiser,*a Kasper S. Pedersen,*b Cinthia Piamonteze,a Stefano Rusponi,c Zaher Salman,d Md.

    Ehesan Ali,e Magnus Schau-Magnussen,b Christian Aa. Thuesen,b Stergios Piligkos,b Høgni

    Weihe,b Hannu Mutka,f Oliver Waldmann,g Peter Oppeneer,h Jesper Bendix,*b Frithjof Nolting,a

    and Harald Brunec

    a Swiss Light Source, Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland. E-mail: jan.dreiser@psi.ch

    b Department of Chemistry, University of Copenhagen, DK-2100 Copenhagen, Denmark. E-mail: ksp@kiku.dk (K.S.P.), bendix@kiku.dk (J.B.)

    c Institute of Condensed Matter Physics, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland.

    d Laboratory for Muon Spin Spectroscopy, Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland.

    e Center for Theoretical Chemistry, Ruhr-Universität Bochum, D-44801, Bochum, Germany.

    f Institut Laue-Langevin, F-38042 Grenoble Cedex 9, France.

    g Physikalisches Institut, Universität Freiburg, D-79104 Freiburg, Germany.

    h Department of Physics and Astronomy, Uppsala University, Box 516, S-751 20 Uppsala, Sweden.

    .

    Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

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    Table of contents

    Experimental Section _____________________________________________________________________________________ 3

    General Procedures and Materials ______________________________________________________________________ 3 Syntheses ____________________________________________________________________________________________________ 3 Crystallography _____________________________________________________________________________________________ 3 SQUID magnetometer measurements ___________________________________________________________________ 4 X-ray magnetic circular dichroism ______________________________________________________________________ 5 Muon-spin relaxation ______________________________________________________________________________________ 5 Inelastic neutron scattering ______________________________________________________________________________ 5 Density-functional theory calculations _________________________________________________________________ 6 Spin-Hamiltonian simulations and fits __________________________________________________________________ 6

    Supplementary Information to the Results Section of the Main Article ________________________ 7 Crystallography: Thermal ellipsoid plots of the crystal structures of 1 and 2 ____________________ 7 X-ray absorption spectroscopy ___________________________________________________________________________ 8 Ligand-field multiplet calculations ______________________________________________________________________ 9 SQUID magnetometry ____________________________________________________________________________________ 10 Inelastic neutron scattering ____________________________________________________________________________ 12 Muon-spin relaxation ____________________________________________________________________________________ 14 Spin-Hamiltonian models _______________________________________________________________________________ 15 Density-functional theory _______________________________________________________________________________ 17

    References ________________________________________________________________________________________________ 17

    Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

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    Experimental Section General Procedures and Materials All chemicals and solvents were purchased from commercial sources and used without further

    purification. [Dy(hfac)3(H2O)2] and trans-[CrF2(py)4]NO3 were prepared as described in the

    literature.1

    Syntheses Synthesis of 1: To a solution of [Dy(hfac)3(H2O)2] (4.0 g, 4.9 mmol) in chloroform (60 ml,

    LabScan; stabilized by 1% ethanol) was added a solution of trans-[CrF2(py)4]NO3 (0.5 g, 1.0 mmol)

    in chloroform (10 ml). The resulting solution was left standing for 12 h to yield needles of

    [Dy(hfac)3(H2O)–CrF2(py)4–Dy(hfac)3(NO3)] which were filtered off and washed with chloroform.

    Yield: 62% (based on Cr). Anal. Calc. (found) for H28C50N5O16F38CrDy2: C: 29.24% (29.13%), H:

    1.37% (1.26%), N: 3.41% (3.33%)

    Synthesis of 2: To a solution of trans-[CrF2(py)4]NO3 (1.2 g, 2.6 mmol) in chloroform (25 ml) was

    added a solution of one equivalent [Dy(hfac)3(H2O)2] (2.1 g, 2.6 mmol) in chloroform (40 ml). Red-

    violet, block-shaped crystals of [Dy(hfac)4–CrF2(py)4]⋅ ½CHCl3 were filtered off after several hours

    and washed with successive aliquots of chloroform. The samples were stored in closed vials in a

    freezer to suppress solvent loss. Yield: 36% (based on Cr), Anal. calc. (found) for

    H24.5C40.5N4O8F26Cl1.5CrDy: C: 33.39% (33.02%), H: 1.70% (1.49%), N: 3.85% (3.90%).

    Crystallography Single-crystal X-ray diffraction data were acquired at 122 K on a Nonius KappaCCD area-detector

    diffractometer, equipped with an Oxford Cryostreams low-temperature device, using graphite-

    monochromated Mo Kα radiation (λ = 0.71073 Å). The structures were solved using direct methods

    (SHELXS97) and refined using the SHELXL97 software package.2 All non-hydrogen atoms were

    refined anisotropically, whereas H-atoms were isotropic and constrained. Crystal structure and

    refinement data for 1 and 2 are summarised in Table S1. The structure of 2 contains a highly

    disordered solvent CHCl3 molecule and no satisfactory model that describes this solvent could be

    achieved. Hence the PLATON SQUEEZE3 procedure was used in the refinement to calculate a

    solvent-accessible void of 311 Å3. It was confirmed that the disordered solvent is located in the void

    volume.

    Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

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    1 2

    Formula C50H28CrDy2F38N5O16 C40H24CrDyF26N4O8

    Mr 2053.77 1397.13

    Color, shape Pink, prism Pink, prism

    crystal size/mm 0.45 × 0.10 × 0.09 0.36 × 0.18 × 0.09

    Crystal system Monoclinic triclinic

    Space group C2/c P-1

    T/K 122 122

    a/Å 26.3208 (13) 12.515 (5)

    b/Å 15.7874 (15) 19.836 (7)

    c/Å 18.718 (3) 21.392 (6)

    α/° 90 85.52 (3)

    β/° 115.474 (9) 81.35 (4)

    γ/° 90 86.229 (19)

    V/Å3 7021.9 (13) 5226 (3)

    Z 4 4

    ρcalc/g cm–3 1.943 1.776

    F000 3956 2720

    µ(Mo Kα)/mm–1 2.42 1.77

    θ range/° 1.6–27.5 1.0–35.0

    collected reflns 73764 299677

    unique reflns 8074 45853

    params/restraints 534/3 1441/0

    reflns (I > 2σ(I)) 6301 33140

    GoF 1.07 1.04

    R1a(I > 2.00σ(I)) 0.041 0.043

    R1a(all data) 0.062 0.073

    wR2b(all data) 0.107 0.095

    max/min Δρ/e Å–3 1.56/−0.84 1.69/−1.27 a R1 = Σ||Fo| – |Fc||/Σ|Fo|. b wR2 = [Σw(Fo2 – Fc2)2/Σw(Fo2)2]1/2

    Table S1: Crystallographic data of 1 and 2.

    SQUID magnetometer measurements The magnetic characterisation was performed on a Quantum-Design MPMS-XL SQUID

    magnetometer equipped with a 5 T dc magnet. The polycrystalline samples were enclosed in frozen

    n-eicosane in polycarbonate capsules. The temperature dependence of the dc magnetic susceptibility

    was determined from magnetisation measurements from 1.8 K to 300 K in a dc field of 100 mT.

    Magnetisation data were acquired at fields up to 5 T and at different temperatures. Data were

    Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

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    corrected for diamagnetic contributions from the sample, n-eicosane and the sample holder by

    means of Pascal´s constants. Ac susceptibility measurements were carried out using an oscillating

    field of 0.3 mT and static dc fields of up to 1 T.

    X-ray magnetic circular dichroism X-ray magnetic circular dichroism (XMCD) measurements were performed at the X-Treme

    beamline at the Swiss Light Source, Paul Scherrer Institut, Switzerland. To prepare the sample,

    polycrystalline powder of 1 was pressed into a piece of Indium mounted on a sample holder. X-ray

    absorption spectra were recorded at a temperature of 2 K in total electron yield mode at the Dy M4,5

    and Cr L2,3 edges. Magnetic fields of up to B = ±6 T along the beam propagation direction were

    applied. The beam was defocused (spot size ~1 × 1 mm2) and kept at very low intensity to avoid

    radiation damage. Scans were taken “on-the-fly”, i.e. the monochromator and insertion device were

    moving continuously while the data were acquired.4 To obtain magnetisation curves, a full

    magnetic-field loop was performed at one polarisation while measuring X-ray absorption at the

    energy of maximum dichroism and at the baseline. Hereafter, the polarisation was changed and

    another loop was run.

    Muon-spin relaxation The µSR measurements were performed on the GPS spectrometer at the Paul Scherrer Institute in

    Switzerland. In these experiments spin-polarised positive muons are imp