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Issue 41, 2011
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Synthesis, structure and magnetic properties of Nd3+ and Pr3+ 2D polymers with tetrafluoro-p-phthalate

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Abstract

Two lanthanide tetrafluoro-p-phthalate (L2−) complexes, Ln(L)1.5·DMF·H2O (Ln = Pr3+ (1), Nd3+ (2)), were synthesized using pyridine as a base. The compounds were found to be isostructural, and the structure of 1 has been determined by single crystal X-ray diffraction (monoclinic, space group C2, a = 22.194(2) Å, b = 11.4347(12) Å, c = 11.7160(12) Å, β = 94.703(2)°, V = 2963.3(5) Å3, Z = 4). The crystal structure of 1 consists of dinuclear Pr3+ units, which are connected by tetrafluoro-p-phthalate, forming separate 2D polymeric layers. The Ln3+ ions in the dinuclear Ln2 units are linked by two μ-O atoms and by two bridging O-C-O groups. The structure is porous with DMF and water molecules located between layers. Non-coordinated DMF molecules occupy about 27% of the unit cell volume. A systematic analysis of reported structures of Ln(III) polymers with p-phthalate and its derivatives shows that the ca. known 60 structures can be divided into six possible structural types depending on the presence of certain structural motifs. The magnetic properties of compounds 1 and 2 were studied. The dependence of χMT on T (where χM is magnetic susceptibility per dinuclear lanthanide unit) for 1 and 2 was simulated using two different models, based on: (i) the Hamiltonian Ĥ = ΔĴz2+ μBgJ, which utilises an axial splitting parameter Δ and temperature-independent paramagnetism (tip) and (ii) crystal field splitting. It was found that both models gave satisfactory fits, indicating that the Ln–Ln exchange interactions are small and the symmetry of the coordination environment is the main factor influencing the magnetic properties of these compounds.

Graphical abstract: Synthesis, structure and magnetic properties of Nd3+ and Pr3+ 2D polymers with tetrafluoro-p-phthalate

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Publication details

The article was received on 28 Jun 2011, accepted on 02 Aug 2011 and first published on 15 Sep 2011


Article type: Paper
DOI: 10.1039/C1DT11237F
Citation: Dalton Trans., 2011,40, 10989-10996
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    Synthesis, structure and magnetic properties of Nd3+ and Pr3+ 2D polymers with tetrafluoro-p-phthalate

    E. A. Mikhalyova, S. V. Kolotilov, M. Zeller, L. K. Thompson, A. W. Addison, V. V. Pavlishchuk and A. D. Hunter, Dalton Trans., 2011, 40, 10989
    DOI: 10.1039/C1DT11237F

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